Patent Number: 048225258
Section: description

In the present invention, by the application of at least one member selected from the group consisting of boric acid, silicic acid, lithium borate, lithium silicate, zinc borate, zinc silicate, an organic silane, a silica sol, an oil emulsion and an alumina sol, such an inorganic acid, inorganic acid salt or organic substance, provides an adhesive effect or a coating film-forming effect, whereby the compression strength and impact strength of the cartridge is improved. As a result, the amount of the dust generated, decreases, and it is possible to prevent troubles caused by the dust. Said at least one member is applied preferably in an amount of from 0.01 to 2% by weight, as solid content, relative to the glass fibers. In the present invention, the inorganic acid or inorganic acid salt such as boric acid, silicic acid, lithium borate, lithium silicate, zinc borate or zinc silicate, or alumina sol, is a component constituting the glass fibers, and therefore can be added without modifying the final composition of glass. Usually, the glass fibers are composed essentially of 55 to 65% by weight of SiO.sub.2, 2 to 6% by weight of B.sub.2 O.sub.3, from 2 to 6% by weight of Li.sub.2 O, from 0 to 6% by weight of BaO, from 2 to 6% by weight of CaO, from 2 to 6% by weight of ZnO and from 2 to 8% by weight of Al.sub.2 O.sub.3. In a particularly preferred example for the glass solidification of radioactive substances, the glass fibers are composed essentially of 60.2% by weight of SiO.sub.2, 19.0% by weight of B.sub.2 O.sub.3, 4.0% by weight of Li.sub.2 O, 4.0% by weight of BaO, 4.0% by weight of CaO, 4.0% by weight of ZnO and 4.8% by weight of Al.sub.2 O.sub.3. The composition of the glass fibers of this type, is relatively strictly determined by its nature. When other components are added, it may happen that no adequate effects are obtainable. Such a possibility can be avoided by using the above-mentioned inorganic acid, inorganic acid salt or alumina sol, because such a material can be added without modifying the composition of the glass fibers. In a more preferred embodiment, the addition of the above-mentioned inorganic acid, inorganic aci salt or alumina sol is adjusted so that the final composition after the addition corresponds to the desired composition of glass fibers. The glass fibers prior to the addition may be composed essentially of 50 to 75% by weight of Si0.sub.2, 0 to 15% by weight of B.sub.2 O.sub.3, from 0 to 10% by weight of Li.sub.2 O, from 0 to 10% by weight of BaO, from 0 to 25% by weight of CaO, from 0 to 10% by weight of ZnO and from 0 to 15% by weight of Al.sub.2 O.sub.3. A boric acid gel or a silicic acid gel may also be employed as the above-mentioned inorganic acid or inorganic acid salt. Among the above-mentioned inorganic acids and acid salts, boric acid (H.sub.3 BO.sub.3) is particularly preferred since it is most inexpensive and readily available. The above-mentioned inorganic acid or inorganic acid salt may be added to the glass fibers, in the form of a solution or powder. Preferably, it is added in the form of a solution. When such an inorganic acid or acid salt is added in the form of a solution, the glass fibers may be dipped in such a solution, or such a solution may be spray-coated onto the glass fibers. The application of the solution of the inorganic acid or inorganic acid salt may be conducted during the fiber-forming step of the glass fibers, or before or after the molding of the fibers into a cartridge, or such different types of applications may be used in combination. With a view to prevention of the generation of a dust, it is preferred to apply the solution after the molding into a cartridge. On the other hand, in the present invention, it is possible to employ an organic silane and an oil emulsion in addition to the above-mentioned inorganic acids, inorganic acid salts and alumina sol. As the organic silane, for example, a .gamma.-alkylaminotriethoxysilane may be used. Likewise, as the oil emulsion, for example, an emulsified mineral oil may be used. By the application of the organic substance capable of imparting the wettability and slipping property to the cartridge itself, such as the organic silane or oil emulsion, during the fiber-forming step, or before or after the molding of the fibers into a cartridge, it is possible to substantially reduce the amount of a dust generated from the cartridge. The organic silane or oil emulsion is applied preferably in an amount of from 0.001 to 1% by weight. More preferably, the amount is from 0.01 to 0.1% by weight, from the view point of the economy and effects. The glass fibers to be used in the present invention, may be short fibers or long fibers. However, the present invention is particularly suitable for short fibers. The average diameter of the glass fibers, is preferably from 8 to 18 .mu.m. If the average diameter is less than 8 .mu.m, it tends to be difficult to obtain a good water-absorbing property. On the other hand, if the average diameter exceeds 18 .mu.m, the productivity in the spinning step tends to be poor, and the fusing points of the glass fibers one another tend to be less, whereby the dimensional stability tends to be poor. The treating capacity of a cartridge is proportional to its weight. In order to increase the amount of the waste liquid to be treated per cartridge, it is therefore necessary to increase the density. In some cases, a product having a density as high as 280 kg/m.sup.3 may be used. The product tends to be susceptible to cracking as the density increases, but cracking may be avoided by improving the manner of handling. The water absorbing property also decreases, but such a decrease does not adversely affect the present invention. Further, the waste liquid tends to hardly penetrate, as the density increases. This can be avoided to some extent by increasing the diameter of the glass fibers to the above-mentioned upper limit of 18 .mu.m. As shown in FIG. 1, glass fibers 11 are deposited on and transported by belt conveyors 12 and 13. During the transportation, an aqueous boric acid solution is applied to the glass fibers 11 by a hot dipping apparatus 14. This hot dipping apparatus 14 is designed so that the aqueous boric acid solution overflowing a supply tube 14a is applied to the glass fibers 11 by a roller 14b. As a separate means, a spray 15 may be employed to apply an aqueous boric acid solution to the glass fibers 11. The concentration of the aqueous boric acid solution may be varied depending upon the temperature of water, and is preferably within a range of from 1 to 10% by weight. Further, it is preferred to conduct heating and drying, for instance, at a temperature of 200.degree. C. for two minutes, after the application of the aqueous boric acid solution, to remove the water. Having thus applied the aqueous boric acid solution to the glass fibers 11, a predetermined amount of the glass fibers 11 is rounded and filled in a mold indicated at 16 and 17, as shown in FIG. 2. The density of the glass fibers 11 is preferably adjusted to a level of from 170 to 270 kg/m.sup.3. If the density is less than 170 kg/m.sup.3, no adequate compression strength is obtainable, and the volume tends to be too large to maintain the glass weight to the impregnated radioactive wast liquid at a proper level, whereby a heat-melting furnace of a large size will be required. On the other hand, if the density exceeds 280 kg/m.sup.3, the cartridge tends to be susceptible to cracking as a whole, whereby no adequate falling strength will be obtained, and the water absorbing property tends to be poor since the spaces between the glass fibers decrease correspondingly. After filling the glass fibers 11 into the mold 16 and 17, the mold is heated at a temperature of 710.degree..+-.15.degree. C. for 35.+-.5 minutes, whereby the glass fibers 11 are partially fused. If the heating temperature is lower than 695.degree. C., or the heating time is shorter than 30 minutes, the fusion of the glass fibers 11 tends to be inadequate, and the moldability tends to be poor. On the other hand, if the heating temperature is higher than 725.degree. C. or the heating time is longer than 40 minutes, the glass fibers 11 are likely to melt and contracted, whereby the water absorbing property will be poor, and the products will be susceptible to cracking. By this heating treatment, boric acid (H.sub.3 BO.sub.3) applied to the glass fibers 11 is converted to B.sub.2 O.sub.3, and B.sub.2 O.sub.3 is melted and coated on the glass fibers 11, whereby an adhesive effect and a coating film-forming effect will be brought about. Further, B.sub.2 O.sub.3 is a component constituting the glass fibers 11, and thus will not adversely affect the performance of the finally obtained cartridge for the disposal of a radioactive waste liquid. After this heat treatment, the mold 16 and 17 is left to cool, and then the glass fibers 11 are taken out to obtain a cartridge 18 as shown in FIG. 3. In this embodiment, the cartridge 18 is of a spherical shape. However, the cartridge may be of a cylinderical shape or of a shape of an angular rod or the like. A cartridge 18 of a spherical shape has the following advantages. Namely, (1) when dumped, the cartridges readily roll, and the frictional resistance is adequately small, whereby the dumping operation can smoothly be conducted, and an automatic operation can readily be accomplished for the waste liquid treatment, (2) clogging scarcely takes place in the dumping installation, and the cartridges are not susceptible to cracking or breakage, whereby the generation of a dust will be minimized, and (3) the cartridges can uniformly be packed, and the heat-melting can be uniformly conducted for the treatment of the radioactive waste liquid. In the present invention, it is preferred that an aqueous boric acid solution is applied by e.g. a spray again to the cartridge 18 thus obtained, followed by heating and drying at a temperature of at least 300.degree. C. By the heating at a temperature of at least 300.degree. C., boric acid (H.sub.3 BO.sub.3) is converted to B.sub.2 O.sub.3. Thus, the generation of a dust can effectively be prevented. The cartridge obtained in the manner as described above, was compared in its performance with a cartridge obtained without conducting the treatment with the aqueous boric acid solution. The results are shown below. ______________________________________ (Boric acid treatment) (Non-treatment) ______________________________________ Compression strength 2 mm 5 mm (Deformation degree) Deviation in 0.3 mm 0.6 mm Compression strength Amount of dust Small Substantial Penetration of Satisfactory Satisfactory waste liquid ______________________________________ Thus, with the cartridge of the present invention treated with boric acid, the strength is high, and the amount of the dust generated, is small. In the above Example, an aqueous boric acid solution was employed. However, it has been found that similar effects are obtainable by using silicic acid, lithium borate, lithium silicate, zinc borate, zinc silicate, an organic silane, an oil emulsion or an alumina sol. As dscribed in the foregoing, according to the present invention by the application of at least one member selected from the group consisting of boric acid, silicic acid, lithium borate, lithium silicate, zinc borate, zinc silicate, an organic silane, an oil emulsion and an alumina sol, to the glass fibers, such an organic acid, organic salt or organic substance provides an adhesive effect or a coating film-forming effect, whereby the compression strength and the impact strength of the cartridge will be improved. As a result, the amount of a dust generated, decreases, and it is possible to prevent troubles caused by the dust.