PatentDe  


Dokumentenidentifikation EP0317774 10.02.1994
EP-Veröffentlichungsnummer 0317774
Titel Kernbrennstoff.
Anmelder General Electric Co., Schenectady, N.Y., US
Erfinder Lay, Kenneth Wilbur, Schenectady New York 12309, US;
Rosenbaum, Herman Solomon, Fremont California 94538, US;
Davies, John Harris, San Jose California 95120, US
Vertreter derzeit kein Vertreter bestellt
DE-Aktenzeichen 3886706
Vertragsstaaten CH, DE, ES, IT, LI, SE
Sprache des Dokument En
EP-Anmeldetag 25.10.1988
EP-Aktenzeichen 881177398
EP-Offenlegungsdatum 31.05.1989
EP date of grant 29.12.1993
Veröffentlichungstag im Patentblatt 10.02.1994
IPC-Hauptklasse G21C 3/62

Beschreibung[en]

In copending European application EP-A-0316623 there is disclosed that a mixture of uranium dioxide and aluminosilicate sintering agent is formed into a compact and sintered to produce a nuclear fuel wherein the uranium dioxide grains have an average grain size of at least about 20 microns and wherein the grains are coated with glassy aluminosilicate phase.

This invention relates to the production of a nuclear fuel body with improved mechanical properties. In one aspect, it is directed to firing a compact of particular composition comprised of uranium dioxide and a magnesium silicate to produce a nuclear fuel of particular microstructure.

Nuclear reactors are presently being designed, constructed and operated in which the fissionable material or nuclear fuel is contained in fuel elements which may have various geometric shapes, such as plates, tubes or rods. Nuclear fuel is enclosed usually in a corrosion-resistant, non-reactive, heat conductive container or clad which as assembled with the nuclear fuel is called a fuel element. The fuel elements are assembled together in a lattice at fixed distances from each other in a coolant flow channel or region forming a fuel assembly, and sufficient fuel assemblies are combined to form the nuclear fission chain reacting assembly or reactor core capable of a self-sustained fission reactor. The core is enclosed within a reactor vessel through which a coolant is passed.

The clad serves two primary purposes: first, to prevent contact and chemical reactions between the nuclear fuel and either the coolant or moderator if present, or both; and second, to prevent the highly radioactive fission products, some of which are gases, from being released from the fuel into the coolant or moderator or both. Common clad materials are stainless steel, aluminum and its alloys, zirconium and its alloys, niobium (columbium), certain magnesium alloys and others. The failure of the clad, due to the buildup of gas pressure or high temperatures in the fuel, or due to corrosion of the clad by deleterious fission products, can contaminate the coolant or moderator and the associated steam systems with intensely radioactive long-lived products to a degree which interferes with plant operation.

The present theoretical and experimental information indicates that a larger grain size in uranium dioxide nuclear fuel will reduce fission gas release rates, a desired attribute which would result in either reduced void space in the fuel rod or an increased design burn-up life for the fuel. Unfortunately, as grain size is increased, the high temperature creep rate of the fuel is reduced - an undesirable result since this gives a greater strain on the clad during a reactor power ramp. Such fuel-induced cladding strain can lead to a cladding failure via a mechanism known as PCI (Pellet Clad Interaction). A fuel with both a larger grain size and an increased creep rate is therefore of interest. Such a fuel is provided by the present invention.

The present nuclear fuel has a microstructure which is useful in avoiding cladding failure. Specifically, the present fuel is a sintered body comprised of uranium dioxide grains having an average size of at least 20 microns whereas the grains are surrounded by a glassy magnesium silicate phase. At an elevated temperature, generally at about 1000°C and higher, the glassy phase increases the creep rate or plasticity of the sintered body significantly above that of uranium dioxide.

Those skilled in the art will gain a further and better understanding of the present invention from the detailed description set forth below, considered in conjunction with the accompanying figure forming a part of the specification which is a transmission electron micrograph of a polished cross-section (magnified 1.050 million x) of the present sintered body showing the glassy magnesium silicate phase as a substantially straight light-colored line.

Briefly stated, the present process for producing a sintered uranium dioxide body wherein the uranium dioxide grains have an average size ranging from 30 to 80 microns and wherein at least 99% by volume of said grains are each coated with glassy magnesium silicate phase leaving no significant portion thereof exposed comprises providing a sinterable uranium dioxide powder containing a fissionable substance, providing a sintering agent composition comprised of from 10 weight % to 55 weight % of MgO balance SiO&sub2; or precursor therefor, admixing said sintering agent composition or precursor therefor with said uranium dioxide powder to give said sintering agent composition ranging from 0.1% by weight to 0.8 by weight of a mixture comprised of said sintering agent composition and uranium dioxide, forming the resulting mixture into a compact, sintering said compact at a temperature at which said sintering agent is a liquid ranging from greater than 1500°C to a temperature at which there is no significant vaporization of SiO&sub2; under conditions wherein the oxygen to uranium atomic ratio ranges from 1.7 to 2.25 to produce a sintered product having said average grain size and cooling said product producing said sintered body, said precursor thermally decomposing below said sintering temperature.

By "glassy" or "glassy magnesium silicate" it is meant herein an amorphous magnesium silicate.

In carrying out the present process, a sinterable uranium dioxide powder is provided containing a fissionable material or substance in an amount effective for making the resulting sintered body useful as nuclear fuel. Representative of such fissionable material is uranium such as U-235 and plutonium such as Pu-239. Normally, uranium dioxide powder contains fissionable isotope of uranium, and frequently it is enriched with such isotope. These powders are known in the art and generally contain fissionable isotope of uranium in an amount ranging from 0.1% by weight to 5% by weight of the total amount of uranium dioxide powder. The uranium dioxide powder has a total oxygen to a total uranium atomic ratio (O/U ratio) ranging from 1.7 to 2.25, frequently from greater than 2.00 to 2.15, depending largely on processing conditions.

Generally, the uranium dioxide powder used in the present process has a specific surface area ranging from 2 to 12 square meters per gram, preferably from 4 to 8 square meters per gram. Such powders allow sintering to be carried out within a reasonable length of time at the present sintering temperature. Uranium dioxide powder having a smaller surface area usually is not useful because it would require sintering temperatures too high to be practical and extraordinary measures to prevent evaporation of SiO&sub2;. On the other hand, uranium dioxide powders having a larger surface area are difficult to handle because of their high chemical reactivity.

The sintering agent is comprised of from 10 weight % to 55 weight % MgO balance SiO&sub2;. In one embodiment, the present sintering agent contains from 10 weight % to 40 weight % MgO, and in another embodiment, it contains from greater than 40 weight % to 55 weight % MgO.

The present sintering agent can be in a number of forms. For example, it can be a combination of MgO and SiO&sub2; powders and/or a magnesium silicate. The magnesium silicate can be a natural material, or it can be produced by a number of techniques such as by melting or solid state sintering of a blend of MgO and SiO&sub2; powders. The natural material can be a mineral preferably predominantly comprised of the present sintering agent. Representative of such natural materials is talc. Specifically, the natural material should be a material which, when fired, but before reaching sintering temperature, has a fired composition comprised of the present magnesium silicate and impurities in an amount of less than 10% by weight of the fired composition. The impurities remaining in the fired composition should have no significant deleterious effect on the present nuclear fuel.

If desired, a particulate precursor for the sintering agent or part thereof can be used provided that it thermally decomposes completely at an elevated temperature below sintering temperature to form the sintering agent or part thereof and by product gas leaving no significant deleterious residue. Magnesium carbonate and magnesium nitrate are useful precursors for magnesium oxide.

The sintering agent is used in an amount ranging from 0.1% by weight to 0.8% by weight of the mixture comprised of uranium dioxide powder and sintering agent. The particular amount of sintering agent used is determinable empirically and depends largely on the particular sintered body desired. Frequently, the present sintering agent ranges from 0.2% by weight to 0.6% by weight, or from 0.25% by weight to 0.5% by weight, of the total weight of the mixture comprised of uranium dioxide and sintering agent. In one embodiment, the sintering agent ranges from 0.1% by weight to less than 0.5% by weight, or from 0.1% by weight or 0.2% by weight to 0.4% by weight, of the mixture comprised of uranium dioxide powder and sintering agent.

The sintering agent and/or source thereof can be admixed with the uranium dioxide powder by a number of conventional techniques, and preferably, they are admixed to form a mixture wherein the sintering agent is dispersed therein preferably at least significantly or substantially uniformly. The sintering agent and/or source thereof is particulate in form and the particles need only be of a size which will form the desired mixture, and generally, they are less than 20 microns.

If desired, a pore-forming additive may also be admixed with the powder to aid in producing the desired porosity in the sintered body. Conventional pore-forming additives can be used such as, for example, ammonium oxalate, polymethyl methacrylate or other materials which volatilize away on heating below sintering temperature. The pore-forming additive can be used in a conventional manner in an effective amount. Generally, the amount of pore-forming additive ranges from 0.1% by weight to 2% by weight of the mixture comprised of uranium dioxide, sintering agent and pore-forming additive.

A number of conventional techniques can be used to shape or press the mixture into a compact. For example, it can be extruded, injection molded, die pressed or isostatically pressed to produce the compact of desired shape. Any lubricants, binders or similar materials used to aid shaping of the mixture should have no significant deleterious effect on the compact or the resulting sintered body. Such shaping-aid materials are preferably of the type which evaporate on heating at relatively low temperatures, preferably below 500°C, leaving no significant residue. Preferably, the compact has a porosity of less than about 60% and more preferably less than about 50% to promote densification during sintering.

The compact can have any desired configuration such as, for example, a pellet, cylinder, plate or square. Typically, the compact is in the form of a cylinder, usually a right cylinder.

The compact is sintered under conditions which will produce the present sintered body. The compact is sintered in an atmosphere which can vary depending largely on the particular manufacturing process. Preferably, the atmosphere is at or about ambient or at or about atmospheric pressure. The compact can be sintered in an atmosphere which is known to be useful for sintering uranium dioxide alone in the production of uranium dioxide nuclear fuel. However, sintering in a vacuum would not be useful since it would tend to vaporize the SiO&sub2;. Generally, the compact is sintered in an atmosphere selected from the group consisting of hydrogen, wet hydrogen preferably having a dewpoint of about 20°C, a controlled atmosphere of a mixture of gases which in equilibrium produces a partial pressure of oxygen sufficient to maintain the uranium dioxide at a desired oxygen to uranium atomic ratio and a combination thereof. Representative of a suitable mixture of gases which in equilibrium produces a partial pressure of oxygen is carbon dioxide and carbon monoxide as disclosed in U.S. 3,927,154 to Carter assigned to the assignee hereof and incorporated herein by reference.

The compact is sintered at a temperature at which the sintering agent forms a liquid phase with the uranium dioxide which enables production of the present liquid phase-sintered body. Generally, the higher the SiO&sub2; content of the sintering agent the lower is the temperature at which the liquid phase forms. The present sintering temperature ranges from above 1500°C to a temperature at which there is no significant vaporization of SiO&sub2;. Generally, it ranges from above 1500°C to 2000°C, preferably from 1540°C to 1750°C, and more preferably from 1600°C to 1700°C.

When the sintering agent contains from 10 weight % to 40 weight % MgO, generally at sintering temperature only solid uranium dioxide and a liquid phase are present. On cooling, generally such liquid phase produces only a glassy magnesium silicate phase. Generally, this glassy phase has a composition which is the same as, or which does not differ significantly from, that of the sintering agent, and it is present in an amount which is the same as, or which does not differ significantly from, the amount of sintering agent used.

However, when the sintering agent contains more than about 40 weight % MgO, generally it produces in the sintered body a glassy phase comprised of from 35 weight % to 45 weight % MgO, frequently about 40 weight % MgO, balance SiO&sub2; and some crystalline magnesium silicate phase. Generally, in this embodiment of the invention, the total amount of glassy and crystalline magnesium silicate phases produced is the same as, or does not differ significantly from, the amount of sintering agent used. Specifically, the total amount of glassy and crystalline magnesium silicate phases generally ranges from 0.1% by weight to 0.8% by weight of the sintered body with the glassy phase component being present in an amount of at least 0.05% by weight of the sintered body, and the crystalline magnesium silicate phase component being present in an amount of at least 0.01% by weight, i.e. an amount detectable by transmission electron microscropy and selected area electron diffraction. Ordinarily, as the MgO content of the sintering agent is increased, the amount of crystalline magnesium silicate present in the sintered body increases.

When the sintering agent contains more than about 40 weight % MgO, it may or may not be totally liquid at sintering temperature. When it is totally liquid, cooling of the liquid phase generally precipitates out some crystalline magnesium silicate and produces a sintered body wherein crystalline magnesium silicate grains are present in the glassy phase in pockets between the coated uranium dioxide grains. However, at lower sintering temperatures and/or higher MgO contents, the sintering agent may produce a liquid phase and also some crystalline magnesium silicate at sintering temperature which results in a sintered body wherein small grains of crystalline magnesium silicate are present in the glassy phase in pockets between the coated uranium dioxide grains and wherein large grains of crystalline magnesium silicate protrude into the coated uranium dioxide grains. The crystalline magnesium silicate grains which protrude into the uranium dioxide grains are significantly larger, usually at least about 20% larger, than crystalline magnesium silicate grains located in the glassy phase. Also, the crystalline magnesium silicate grains which protrude into the uranium dioxide grains generally are present in an amount of less than about 50% by volume of the total amount of crystalline magnesium silicate phase present in the sintered body. The crystalline magnesium silicate phase is selected from the group consisting of MgSiO&sub3;, Mg&sub2;SiO&sub4; and a mixture thereof.

The compact is maintained at sintering temperature for a time required to produce the present sintered body. Time at sintering temperature is determinable empirically depending largely on the particular sintered body desired. Generally, the grain size of uranium dioxide in the sintered body is determined by sintering temperature, time at sintering temperature and by the sintering agent. Ordinarily, the higher the sintering temperature and/or the longer the time at sintering temperature, the larger are the uranium dioxide grains. Higher magnesium oxide contents in the sintering agent also result in larger uranium dioxide grains.

The rate of heating to sintering temperature is limited largely by how fast any by-product gases are removed prior to sintering and generally this depends on the gas flow rate through the furnace and its uniformity therein as well as the amount of material in the furnace. Generally, a rate of heating of from about 50°C per hour to about 300°C per hour is used until by-product gases have been removed from the furnace, and this may be determined empirically by standard techniques. The rate of heating can then be increased, if desired, to a range of about 300°C to 500°C per hour and as high as 800°C per hour but should not be so rapid as to crack the bodies.

Upon completion of sintering, the sintered product is cooled to produce the present sintered body, and usually it is cooled to ambient or to about room temperature, generally about 20°C to 30°C. The rate of cooling of the sintered product or body is not critical, but it should not be so rapid as to crack the body. Specifically, the rate of cooling can be the same as the cooling rates normally or usually used in commercial sintering furnaces. These cooling rates may range from about 100°C to about 800°C per hour. The sintered product or body can be cooled in the same atmosphere in which it was sintered or a different atmosphere which has no significant deleterious effect thereon.

In one embodiment, the present sintered body is comprised of crystalline uranium dioxide grains and an amorphous glassy magnesium silicate phase comprised of from 10 weight % to 40 weight % MgO balance SiO&sub2;. In this embodiment, the glassy phase ranges from 0.1% by weight to 0.8% by weight of the sintered body. Frequently, it ranges from 0.2% by weight to 0.6% by weight, or from 0.25% by weight to 0.5% by weight, or from 0.1% by weight to less than 0.5% by weight, or from 0.1% by weight or 0.2% by weight to 0.4% by weight, of the sintered body.

In another embodiment, the present sintered body is comprised of crystalline uranium dioxide, glassy magnesium silicate phase comprised of from 35 weight % to 45 weight % MgO, frequently about 40 weight % MgO, balance SiO&sub2; and crystalline magnesium silicate phase, with the crystalline magnesium silicate phase being present in at least 0.01% by weight and the glassy phase being present in an amount of at least about 0.05% by weight of the body. Generally, in this embodiment, the total amount of glassy and crystalline magnesium silicate phases is the same as, or does not differ significantly from, the amount of sintering agent used. Specifically, the total amount of glassy and crystalline magnesium silicate phases ranges from 0.1% by weight to 0.8% by weight, or from 0.2% by weight to 0.6% by weight, or from 0.25% by weight to 0.5% by weight, or from 0.1% by weight to less than 0.5% by weight, or from 0.1% by weight or 0.2% by weight to 0.4% by weight, of the sintered body. Frequently, the glassy phase component is present in an amount greater than 0.05% by weight, or greater than 0.1% by weight, or greater than 0.2% by weight of the sintered body. Also, frequently, the crystalline magnesium silicate phase component is present in an amount of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.2% by weight, of the sintered body.

The present sintering agent in an amount of less than 0.1% by weight may not produce the present sintered body. On the other hand, the sintering agent in an amount greater than 1% by weight produces an excessive amount of glassy and/or crystalline magnesium silicate phases which provide no significant advantage, and which would occupy space that could usefully be occupied by uranium dioxide.

Generally, the glassy phase in the sintered body is free of uranium dioxide. However, it is possible that in some instances some uranium dioxide might be present in the glassy phase in a minor amount detectable by exotic analysis not believed to be presently available, and in such instances, the uranium dioxide ordinarily would range up to 0.5% by weight of the glassy phase.

The glassy magnesium silicate phase in the sintered body is a continuous interconnecting phase. The glassy phase coats each uranium dioxide grain leaving no significant portion thereof exposed of at least 99% by volume, preferably more than 99.5% by volume, of the total volume of uranium dioxide grains in the sintered body. Most preferably, it coats every uranium dioxide grain leaving no significant portion thereof exposed. By a glassy phase which coats a uranium dioxide grain leaving no significant portion thereof exposed it is meant a coating which covers at least substantially all of the grain. Specifically, the glassy phase forms a thin continuous adherent coating on each uranium dioxide grain it coats which generally ranges from 5 to 20 × 10&supmin;¹&sup0; m (5 to 20 Angstroms) in thickness. In a preferred embodiment, the glassy phase coats each uranium dioxide grain totally, i.e. it totally envelops, each uranium dioxide grain of at least 99% by volume, preferably more than 99.5% by volume, of the total volume of uranium dioxide grains in the sintered body. More preferably, the glassy phase coats every uranium dioxide grain totally. The glassy magnesium silicate phase also extends to some degree into the interstices, i.e. 3-grain and 4-grain interstices, between the coated uranium dioxide grains. The extent to which the glassy phase fills the interstices depends largely on the amount of sintering agent in the sintered body. The morphology of the microstructure of the sintered body indicates that the glassy magnesium silicate phase was a liquid at sintering temperature.

The uranium dioxide grains in the sintered body have an average grain size, i.e. average diameter, ranging from 20 microns to 100 microns, preferably from 30 microns to 80 microns, frequently from 40 microns to 70 microns, and more frequently from about 45 microns to about 60 microns. In one embodiment of the present invention, the uranium dioxide grains do not differ significantly in size.

The average grain size can be determined in a standard manner. In the present invention a standard line intercept technique was used. Specifically, a line was drawn on a photomicrograph of a polished and etched cross-section of the sintered body, and the grain boundaries intercepting along a specific length of line were counted and divided into that specific length of line to give an average grain intercept length in terms of microns. That value was then multiplied by 1.5 to determine the average grain size.

The present sintered body has the appearance of having been liquid phase sintered. The uranium dioxide grain corners as viewed in a polished section often appear rounded with glassy phase pockets located at the grain corner, i.e. they have the appearance of a liquid phase sintered ceramic. Generally, the uranium dioxide grains are equiaxed or substantially equiaxed.

The present sintered body generally is free of crystalline phases of MgO and SiO&sub2;.

The present sintered body always contains some porosity which generally is a closed porosity, i.e. non-interconnecting pores. The porosity is distributed through the sintered body, and preferably, it is distributed at least significantly or substantially uniformly. Generally, the porosity of the sintered body ranges from 2% by volume to less than 10% by volume of the sintered body depending largely on reactor design. Frequently, the porosity ranges from 4% by volume to 8% by volume, more frequently from 4% by volume to 6% by volume, and most frequently 5% by volume, of the total volume of the sintered body. Preferably, the pores range in size from greater than 1 micron to 20 microns, and more preferably from 5 microns to 20 microns.

Ordinarily, the dimensions of the present sintered body differ from those of the unsintered body by the extent of shrinkage, i.e. densification, which occurs during sintering.

A magnesium silicate outside the present range is not operable as a sintering agent to produce the present sintered body. Generally, a magnesium silicate containing more than about 90 weight % SiO&sub2; will produce a sintered body with too small a grain size. On the other hand, a magnesium silicate containing MgO in an amount of more than about 55 weight % generally is not useful because the amount of the glassy phase usually is too small with most of the sintering agent present as crystalline magnesium silicate.

SiO&sub2; alone is not useful as a sintering agent because it produces a sintered body with too small a grain size, and the glassy phase formed does not distribute itself uniformly throughout the sintered body. Likewise, MgO alone would leave crystalline MgO in the sintered body. Crystalline phases do not impart plasticity at elevated temperature to a sintered uranium dioxide body which is significantly higher than that of uranium dioxide alone.

The present sintered body is useful as a nuclear fuel. It contains fissionable material generally in the same amount present in the uranium dioxide powder. The large grain size of the present sintered body should significantly lower fission gas release rates. Also, the glassy phase coating the uranium dioxide grains imparts to the sintered body a plasticity or creep rate which allows the fuel to perform without putting significant stress on the cladding.

The invention is further illustrated by the following example wherein the procedure was as follows, unless otherwise stated:

Submicron sinterable uranium dioxide powder containing a fissionable isotope of uranium and having an oxygen to uranium atomic ratio of about 2.16 was used.

The sintering agent was particulate in form.

The sintering agent was admixed with the uranium dioxide powder in a standard manner by stirring to produce a substantially uniform mixture.

The mixture of uranium dioxide powder and sintering agent was die pressed in a steel die to give a green body in pellet form, i.e. a compact in the form of a roughly equiaxed cylinder with a porosity of about 50%.

The sintering atmosphere was hydrogen at or about atmospheric pressure.

Density was determined in a standard manner by weighing the sintered body and measuring its dimensions.

Porosity of the sintered body was determined by knowing or estimating the theoretical density of the sintered body on the basis of its composition and comparing that to the density measured using the following equation:

   Average uranium dioxide grain size of the sintered body was determined by the line intercept method disclosed herein.

The sintered body was characterized by a number of standard techniques.

Based on other work, it was known that the sintered body had an oxygen to uranium atomic ratio of about 2.00.

EXAMPLE 1

The sintering agent was comprised of 35 weight % MgO powder and 65 weight % SiO&sub2; powder.

The sintering agent was admixed with the uranium dioxide powder to produce a substantially uniform mixture containing the sintering agent in an amount of 0.1% by weight of the total mixture.

The mixture was pressed into a compact. The compact was sintered at about 1640°C for 7 hours and then furnace-cooled to about room temperature. A cross-section of the sintered body was mechanically thinned, ion-milled, and examined by transmission electron microscopy. It was comprised of uranium dioxide grains and a thin intergranular glassy phase. A transmission electron micrograph showing the thin intergranular glass phase is shown in the figure. Based on other work, it was known that the glassy phase was a magnesium silicate comprised of about 35 weight % MgO and about 65 weight % SiO&sub2; and that the total amount of glassy phase in the sintered body did not differ significantly from the amount of sintering agent used. Also, based on other work, it was known that the glassy phase was continuous, interconnecting and coated each uranium dioxide grain of more than 99% by volume of the uranium dioxide grains leaving no significant portion thereof exposed.

The sintered body had a porosity of about 2.6% by volume which was comprised of closed pores distributed in the body.

The uranium dioxide grains did not differ significantly in size and had an average size of about 22 microns.

The sintered body is useful as nuclear fuel. Based on other work, it is known that the creep rate of this sintered body should increase rapidly with stress and should be substantially higher than that reported in the literature for similar sintered bodies of uranium dioxide alone of smaller average grain size. The high deformation rate of the present nuclear fuel will allow the fuel to perform without putting significant sustained stress on the cladding.

Also, the larger grain size of the present fuel should result in significantly lower fission gas release rates.


Anspruch[de]
  1. Verfahren zum Herstellen eines gesinterten Urandioxid-Körpers, der als Kernbrennstoff brauchbar ist, worin die Urandioxid-Körner eine mittlere Korngröße von 30 bis 80 µm haben und worin mindestens 99 Vol.-% der Urandioxid-Körner jeweils mit glasartiger Magnesiumsilicat-Phase überzogen sind, die keinen wesentlichen Teil davon unbedeckt läßt, wobei der Körper eine Porosität im Bereich von 2 Vol.-% bis weniger als 10 Vol.-% hat, umfassend:

    Schaffen von Urandioxid-Pulver, enthaltend eine spaltbare Substanz,

    Schaffen einer Sintermittelzusammensetzung, zusammengesetzt aus 10 Gew.-% bis 55 Gew.-% MgO, Rest SiO&sub2; oder einem Vorläufer dafür,

    Vermischen der Sintermittel-Zusammensetzung mit dem Urandioxid, so daß die Sintermittel-Zusammensetzung 0,1 Gew.-% bis 0,8 Gew.-% einer sinterbaren Mischung ausmacht, die aus Sintermittel-Zusammensetzung und Urandioxid zusammengesetzt ist,

    Formen der resultierenden Mischung zu einem Preßling, Sintern des Preßlings bei einer Temperatur, bei der das Sintermittel eine flüssige Phase bildet, im Bereich von mehr als 1500°C bis zu einer Temperatur, bei der keine bedeutende Verdampfung des SiO&sub2; unter Bedingungen stattfindet, bei denen das Atomverhältnis von Sauerstoff zu Uran im Bereich von 1,7 bis 2,25 liegt, um ein Sinterprodukt herzustellen, das die genannte mittlere Korngröße hat und

    Abkühlen des Produktes zur Herstellung des Sinterkörpers, wobei sich der Vorläufer unterhalb der Sintertemperatur thermisch zersetzt.
  2. Verfahren nach Anspruch 1, worin das Atomverhältnis von Sauerstoff zu Uran im Bereich von 2,00 bis 2,15 liegt.
  3. Verfahren nach Anspruch 1, worin die Porosität des Sinterkörpers im Bereich von 4 Vol.-% bis 8 Vol.-% des Sinterkörpers liegt.
  4. Verfahren nach Anspruch 1, worin die Sintermittel-Zusammensetzung im Bereich von 0,2 Gew.-% bis 0,4 Gew.-% der sinterbaren Mischung vorhanden ist.
  5. Verfahren nach Anspruch 1, worin das Sintermittel im Bereich von 0,1 Gew.-% bis 0,2 Gew.-% der sinterbaren Mischung liegt.
  6. Verfahren nach Anspruch 1, worin das Sintermittel im Bereich von 0,2 Gew.-% bis 0,6 Gew.-% der sinterbaren Mischung liegt.
  7. Verfahren nach Anspruch 1, worin das Sintermittel im Bereich von 0,1 Gew.-% bis weniger als 0,5 Gew.-% der sinterbaren Mischung liegt.
  8. Verfahren nach Anspruch 1, worin das Sintermittel zusammengesetzt ist aus 10 Gew.-% bis 40 Gew.-% MgO, Rest SiO&sub2;.
  9. Verfahren nach Anspruch 1, worin das Sintermittel zusammengesetzt ist aus mehr als 40 Gew.-% bis 55 Gew.-% MgO, Rest SiO&sub2;.
  10. Verfahren nach Anspruch 1, worin die Sintertemperatur im Bereich von 1540°C bis 1800°C liegt.
  11. Verfahren nach Anspruch 3, worin der Vorläufer Magnesiumcarbonat ist.
  12. Verfahren nach Anspruch 1, worin das Sintern in einer gasförmigen Atmosphäre feuchten Wasserstoffes ausgeführt wird.
  13. Verfahren nach Anspruch 1, worin das Sintern in einer gasförmigen Atmosphäre ausgeführt wird, die aus einer Mischung von Kohlendioxid und Kohlenmonoxid zusammengesetzt ist.
  14. Verfahren nach Anspruch 1, worin die mittlere Korngröße des Urandioxids im Bereich von 30 µm bis 70 µm liegt.
  15. Kernbrennstoffkörper, zusammengesetzt aus kristallinen Urandioxid-Körnern und einer amorphen glasartigen Phase von Magnesiumsilicat, wobei die Urandioxid-Körner eine mittlere Größe im Bereich von 30 µm bis 80 µm und ein Atomverhältnis von Sauerstoff zu Uran von 1,7 bis 2,25 haben, die glasartige Phase zusammenhängend und verbindend ist, jedes Korn von mindestens etwa 99 Vol.-% der Urandioxidkörner mit der glasartigen Phase überzogen ist, was keinen bedeutenden Teil davon unbedeckt läßt, die glasartige Phase im Bereich von 0,1 Gew.-% bis 0,8 Gew.-% des Körpers vorhanden ist, der Körper eine Porosität im Bereich von 2 Vol.-% bis weniger als 10 Vol.-% des Körpers hat.
  16. Körper nach Anspruch 15, worin die glasartige Phase zusammengesetzt ist aus 10 Gew.-% bis 40 Gew.-% MgO, Rest SiO&sub2;.
  17. Körper nach Anspruch 15, worin die Porosität im Bereich von 4 Vol.-% bis 8 Vol.-% des Körpers liegt.
  18. Körper nach Anspruch 15, worin die mittlere Größe der Urandioxid-Körner im Bereich von 30 µm bis 70 µm liegt.
  19. Körper nach Anspruch 15, worin die glasartige Magnesiumsilicatphase im Bereich von 0,1 Gew.-% bis weniger als 0,5 Gew.-% des Körpers liegt.
  20. Kernbrennstoff-Körper, zusammengesetzt aus kristallinen Urandioxid-Körnern, einer amorphen glasartigen Magnesiumsilicat-Phase und kristalliner Magnesiumsilicat-Phase, wobei die Urandioxid-Körner eine mittlere Größe im Be-reich von 30 µm bis 80 µm und ein Atomverhältnis von Sauerstoff zu Uran von 1,7 bis 2,25 haben, die glasartige Phase zusammenhängend und verbindend ist, jedes Korn von mindestens 99 Vol.-% der Urandioxid-Körner durch die glasartige Phase überzogen ist, was keinen bedeutenden Teil davon unbedeckt läßt, die Gesamtmenge der glasartigen und kristallinen Magnesiumsilicat-Phasen im Bereich von 0,1 Gew.-% bis 0,8 Gew.-% des Körpers liegt, die glasartige Phase in einer Menge von mindestens 0,05 Gew.-% des Körpers vorhanden ist, die kristalline Magnesiumsilicat-Phase in einer Menge von mindestens 0,01 Gew.-% des Körpers vorhanden ist, der Körper eine Porosität im Bereich von 2 Vol.-% bis weniger als 10 Vol.-% des Körpers aufweist.
  21. Kernbrennstoff-Körper nach Anspruch 20, worin die kristalline Magnesiumsilicat-Phase in der glasartigen Phase in Taschen zwischen den überzogenen Urandioxid-Körnern vorhanden ist.
  22. Kernbrennstoff-Körper nach Anspruch 21, worin die kristalline Magnesiumsilicat-Phase auch in die überzogenen Urandioxid-Körner vorsteht.
  23. Kernbrennstoff-Körper nach Anspruch 20, worin die glasartige Phase zusammengesetzt ist aus 35 Gew.-% bis 45 Gew.-% MgO, Rest SiO&sub2;.
  24. Kernbrennstoff-Körper nach Anspruch 20, worin das kristalline Silicat ausgewählt ist aus der Gruppe bestehend aus MgSiO&sub3;, Mg&sub2;SiO&sub4; und einer Mischung daraus.
  25. Kernbrennstoff-Körper nach Anspruch 20, worin die Porosität im Bereich von 4 Vol.-% bis 8 Vol.-% des Körpers liegt.
  26. Kernbrennstoff-Körper nach Anspruch 20, worin die mittlere Größe der Urandioxid-Körner im Bereich von 30 µm bis 70 µm liegt.
  27. Verfahren nach einem der Ansprüche 1 bis 14, worin ein natürliches Material benutzt wird, das Sintermittel zu schaffen, wobei das Material nach dem Glühen unterhalb der Sintertemperatur eine Glühzusammensetzung hat, die im wesentlichen aus dem Sintermittel und Verunreinigungen in einer Menge von weniger als 10 Gew.-% der Glühzusammensetzung besteht.
Anspruch[en]
  1. A process for producing a sintered uranium dioxide body useful as nuclear fuel wherein the uranium dioxide grains have an average grain size ranging from 30 to 80 microns and wherein at least 99% by volume of the uranium dioxide grains are each coated with glassy magnesium silicate phase leaving no significant portion thereof exposed, said body having a porosity ranging from 2% by volume to less than 10% by volume, which comprises providing uranium dioxide powder containing a fissionable substance, providing a sintering agent composition comprised of from 10 weight % to 55 weight % MgO balance SiO&sub2; or precursor therefor, admixing said sintering agent composition or precursor therefor with said uranium dioxide to give said sintering agent composition ranging from 0.1% by weight to 0.8% by weight of a sinterable mixture comprised of said sintering agent composition and uranium dioxide, forming the resulting mixture into a compact, sintering said compact at a temperature at which said sintering agent forms a liquid phase ranging from greater than 1500°C to a temperature at which there is no significant vaporization of said SiO&sub2; under conditions wherein the oxygen to uranium atomic ratio ranges from 1.7 to 2.25 to produce a sintered product having said average grain size and cooling said product to produce said sintered body, said precursor thermally decomposing below said sintering temperature.
  2. The process according to Claim 1 wherein said oxygen to uranium atomic ratio ranges from 2.00 to 2.15.
  3. The process according to Claim 1 wherein said porosity of said sintered body ranges from 4% by volume to 8% by volume of said sintered body.
  4. The process according to Claim 1 wherein said sintering agent composition ranges from 0.2% by weight to 0.4% by weight of said sinterable mixture.
  5. The process according to Claim 1 wherein said sintering agent composition ranges from 0.1% by weight to 0.2% by weight of said sinterable mixture.
  6. The process according to Claim 1 wherein said sintering agent composition ranges from 0.2% by weight to 0.6% by weight of said sinterable mixture.
  7. The process according to Claim 1 wherein said sintering agent composition ranges from 0.1% by weight to less than 0.5% by weight of said sinterable mixture.
  8. The process according to Claim 1 wherein said sintering agent is comprised of from 10 weight % to 40 weight % MgO balance SiO&sub2;.
  9. The process according to Claim 1 wherein said sintering agent is comprised of from greater than 40 weight % to 55 weight % MgO balance SiO&sub2;.
  10. The process according to Claim 1 wherein said sintering temperature ranges from 1540°C to 1800°C.
  11. The process according to Claim 1 wherein said precursor is magnesium carbonate.
  12. The process according to Claim 1 wherein said sintering is carried out in a gaseous atmosphere of wet hydrogen.
  13. The process according to Claim 1 wherein said sintering is carried out in a gaseous atmosphere comprised of a mixture of carbon dioxide and carbon monoxide.
  14. The process according to Claim 1 wherein said average grain size of uranium dioxide ranges from 30 microns to 70 microns.
  15. A nuclear fuel body comprised of crystalline uranium dioxide grains and an amorphous glassy phase of magnesium silicate, said uranium dioxide grains having an average size ranging from 30 microns to 80 microns and an oxygen to uranium atomic ratio of from 1.7 to 2.25, said glassy phase being continuous and interconnecting, each grain of at least 99% by volume of said uranium dioxide grains being coated with said glassy phase leaving no significant portion thereof exposed, said glassy phase ranging from 0.1% by weight to 0.8% by weight of said body, said body having a porosity ranging from 2% by volume to less than 10% by volume of said body.
  16. The body according to Claim 15 wherein said glassy phase is comprised of from 10 weight % to 40 weight % MgO balance SiO&sub2;.
  17. The body according to Claim 15 wherein said porosity ranges from 4% by volume to 8% by volume of said body.
  18. The body according to Claim 15 wherein said average size of said uranium dioxide grains ranges from 30 microns to 70 microns.
  19. The body according to Claim 15 wherein said glassy magnesium silicate phase ranges from 0.1% by weight to less than 0.5% by weight of said body.
  20. A nuclear fuel body comprised of crystalline uranium dioxide grains, an amorphous glassy magnesium silicate phase and crystalline magnesium silicate phase, said uranium dioxide grains having an average size ranging from 30 microns to 80 microns and an oxygen to uranium atomic ratio of 1.7 to 2.25, said glassy phase being continuous and interconnecting, each grain of at least 99% by volume of said uranium dioxide grains being coated by said glassy phase leaving no significant portion thereof exposed, the total amount of said glassy and crystalline magnesium silicate phases ranging from 0.1% by weight to 0.8% by weight of said body, said glassy phase being present in an amount of at least 0.05% by weight of said body, said crystalline magnesium silicate phase being present in an amount of at least 0.01% by weight of said body, said body having a porosity ranging from 2% by volume to less than 10% by volume of said body.
  21. The nuclear fuel body according to Claim 20 wherein said crystalline magnesium silicate phase is present in said glassy phase in pockets between said coated uranium dioxide grains.
  22. The nuclear fuel body according to Claim 21 wherein said crystalline magnesium silicate phase also protrudes into said coated uranium dioxide grains.
  23. The nuclear fuel body according to Claim 20 wherein said glassy phase is comprised of from 35 weight % to 45 weight % MgO balance SiO&sub2;.
  24. The nuclear fuel body according to Claim 20 wherein said crystalline magnesium silicate is selected from the group consisting of MgSiO&sub3;, Mg&sub2;SiO&sub4; and a mixture thereof.
  25. The nuclear fuel body according to Claim 20 wherein said porosity ranges from 4% by volume to 8% by volume of said body.
  26. The nuclear fuel body according to Claim 20 wherein said average size of said uranium dioxide grains ranges from 30 microns to 70 microns.
  27. The process according to any of claims 1-14 wherein a natural material is used to provide said sintering agent, said material when fired but below said sintering temperature having a fired composition consisting essentially of said sintering agent and impurities in an amount of less than 10% by weight of the fired composition.
Anspruch[fr]
  1. Procédé de production d'un élément fritté en dioxyde d'uranium, utile comme combustible nucléaire, dans lequel les grains de dioxyde d'uranium ont une taille moyenne de grain de 30 à 80 microns et dans lequel au moins 99% en volume des grains de dioxyde d'uranium sont revêtus d'une phase vitreuse de silicate de magnésium, qui ne laisse pas de partie notable desdits grains exposée, ledit élément ayant une porosité comprise dans l'intervalle allant de 2% en volume à moins de 10% en volume, procédé qui comprend la fourniture d'une poudre de dioxyde d'uranium renfermant un produit fissile, la fourniture d'une composition d'agent de frittage, contenant de 10% en poids à 55% en poids de MgO, le complément étant constitué de SiO&sub2;, ou d'un précurseur de cette composition, le mélange de ladite composition d'agent de frittage ou de son précurseur avec ledit dioxyde d'uranium, pour l'obtention d'un mélange frittable, constitué de ladite composition d'agent de frittage et du dioxyde d'uranium, la teneur en ladite composition d'agent de frittage dudit mélange étant comprise dans l'intervalle allant de 0,1% en poids à 0,8% en poids, la mise du mélange résultant sous une forme compacte, le frittage de ladite forme compacte à une température à laquelle ledit agent de frittage forme une phase liquide, ladite température étant comprise dans l'intervalle allant d'une température supérieure à 1500°C jusqu'à une température à laquelle il n'y a pas de vaporisation notable dudit SiO&sub2;, dans des conditions où le rapport en atomes de l'oxygène à l'uranium est compris dans l'intervalle allant de 1,7 à 2,25, pour la production d'un produit fritté ayant ladite taille moyenne de grain, et le refroidissement dudit produit pour la production dudit élément fritté, ledit précurseur se décomposant thermiquement à une température inférieure à ladite température de frittage.
  2. Procédé selon la revendication 1, dans lequel ledit rapport en atomes de l'oxygène à l'uranium est compris dans l'intervalle allant de 2,00 à 2,15.
  3. Procédé selon la revendication 1, dans lequel ladite porosité dudit élément fritté est comprise dans l'intervalle allant de 4% en volume à 8% en volume dudit élément fritté.
  4. Procédé selon la revendication 1, dans lequel ladite composition d'agent de frittage représente de 0,2% en poids à 0,4% en poids dudit mélange frittable.
  5. Procédé selon la revendication 1, dans lequel ladite composition d'agent de frittage représente de 0,1% en poids à 0,2% en poids dudit mélange frittable.
  6. Procédé selon la revendication 1, dans lequel ladite composition d'agent de frittage représente de 0,2% en poids à 0,6% en poids dudit mélange frittable.
  7. Procédé selon la revendication 1, dans lequel ladite composition d'agent de frittage représente de 0,1% en poids à moins de 0,5% en poids dudit mélange frittable.
  8. Procédé selon la revendication 1, dans lequel ledit agent de frittage contient de 10% en poids à 40% en poids de MgO, le complément étant constitué de SiO&sub2;.
  9. Procédé selon la revendication 1, dans lequel ledit agent de frittage contient de plus de 40% en poids jusqu'à 55% en poids de MgO, le complément étant constitué de SiO&sub2;.
  10. Procédé selon la revendication 1, dans lequel ladite température de frittage est comprise dans l'intervalle allant de 1540°C à 1800°C.
  11. Procédé selon la revendication 1, dans lequel ledit précurseur est du carbonate de magnésium.
  12. Procédé selon la revendication 1, dans lequel on réalise ledit frittage dans une atmosphère gazeuse, constituée d'hydrogène humide.
  13. Procédé selon la revendication 1, dans lequel on réalise ledit frittage dans une atmosphère gazeuse, constituée d'un mélange de dioxyde de carbone et de monoxyde de carbone.
  14. Procédé selon la revendication 1, dans lequel ladite taille moyenne de grain du dioxyde d'uranium est comprise dans l'intervalle allant de 30 microns à 70 microns.
  15. Elément de combustible nucléaire, contenant des grains de dioxyde d'uranium cristallins et une phase amorphe vitreuse, constituée de silicate de magnésium, lesdits grains de dioxyde d'uranium ayant une taille moyenne de 30 microns à 80 microns et présentant un rapport en atomes de l'oxygène à l'uranium de 1,7 à 2,25, ladite phase vitreuse étant continue et réalisant une interconnexion, chaque grain d'au moins 99% en volume desdits grains de dioxyde d'uranium étant revêtu de ladite phase vitreuse, qui ne laisse pas de partie notable dudit grain exposée, ladite phase vitreuse représentant de 0,1% en poids à 0,8% en poids dudit élément, ledit élément ayant une porosité comprise dans l'intervalle allant de 2% en volume à moins de 10% en volume dudit élément.
  16. Elément selon la revendication 15, dans lequel ladite phase vitreuse contient de 10% en poids à 40% en poids de MgO, le complément étant constitué de SiO&sub2;.
  17. Elément selon la revendication 15, pour lequel ladite porosité est comprise dans l'intervalle allant de 4% en volume à 8% en volume dudit élément.
  18. Elément selon la revendication 15, dans lequel ladite taille moyenne desdits grains de dioxyde d'uranium est comprise dans l'intervalle allant de 30 microns à 70 microns.
  19. Elément selon la revendication 15, dans lequel ladite phase vitreuse de silicate de magnésium représente de 0,1% en poids à moins de 0,5% en poids dudit élément.
  20. Elément de combustible nucléaire, contenant des grains de dioxyde d'uranium cristallins, une phase amorphe vitreuse, constituée de silicate de magnésium, et une phase cristalline de silicate de magnésium, lesdits grains de dioxyde d'uranium ayant une taille moyenne de 30 microns à 80 microns et présentant un rapport en atomes de l'oxygène à l'uranium de 1,7 à 2,25, ladite phase vitreuse étant continue et réalisant une interconnexion, chaque grain d'au moins 99% en volume desdits grains de dioxyde d'uranium étant revêtu de ladite phase vitreuse, qui ne laisse pas de partie notable dudit grain exposeé, la proportion totale desdites phases vitreuse et cristalline de silicate de magnésium représentant de 0,1% en poids à 0,8% en poids dudit élément, ladite phase vitreuse étant présente en une proportion d'au moins 0,05% en poids dudit élément, ladite phase cristalline de silicate de magnésium étant présente en une proportion d'au moins 0,01% en poids dudit élément, ledit élément ayant une porosité comprise dans l'intervalle allant de 2% en volume à moins de 10% en volume dudit élément.
  21. Elément de combustible nucléaire selon la revendication 20, dans lequel ladite phase cristalline de silicate de magnésium est présente dans ladite phase vitreuse, dans des poches situées entre lesdits grains de dioxyde d'uranium revêtus.
  22. Elément de combustible nucléaire selon la revendication 21, dans lequel ladite phase cristalline de silicate de magnésium fait également saillie dans lesdits grains de dioxyde d'uranium revêtus.
  23. Elément de combustible nucléaire selon la revendication 20, dans lequel ladite phase vitreuse contient de 35% en poids à 45% en poids de MgO, le complément étant constitué de SiO&sub2;.
  24. Elément de combustible nucléaire selon la revendication 20, dans lequel ledit silicate de magnésium cristallin est choisi parmi MgSiO&sub3;, Mg&sub2;SiO&sub4; et leurs mélanges.
  25. Elément de combustible nucléaire selon la revendication 20, pour lequel ladite porosité est comprise dans l'intervalle allant de 4% en volume à 8% en volume dudit élément.
  26. Elément de combustible nucléaire selon la revendication 20, dans lequel ladite taille moyenne desdits grains de dioxyde d'uranium est comprise dans l'intervalle allant de 30 microns à 70 microns.
  27. Procédé selon l'une quelconque des revendications 1 à 14, dans lequel on utilise un produit naturel pour fournir ledit agent de frittage, ledit produit ayant, lorsqu'il est calciné à une température inférieure à ladite température de frittage, une composition à l'état calciné, constituée essentiellement dudit agent de frittage et d'impureté en une proportion inférieure à 10% en poids de la composition à l'état calciné.






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