the present invention is of a method of making nanostructured glass - ceramic waste forms that can be used for disposition of various radionuclides , especially iodine , and of the resulting waste form . the method is based on the previous invention of using mesoporous alumina and its derivatives as getter materials for entrapping gaseous iodine ( u . s . patent application ser . no . 12 / 127 , 111 ). in the present invention , iodine sorbed on mesoporous material is first fixed with sodium silicate to convert molecular iodine into less volatile ionic species . the resulting material is then vitrified with additional glass - forming components so that iodine forms nanometer precipitates that are encapsulated in either a glass or a crystalline matrix . the loss of iodine , for example , during vitrification is minimal (˜ 0 %). the preferred vitrification temperature is about 850 - 950 ° c . this temperature is lower than that generally used for glass formation ( higher than about 1100 ° c .). the method of the invention does not require using silver for immobilizing iodine , thus reducing the cost of waste form development as well as the potential environmental hazards related to waste form production disposal . fixation of nuclide - loaded getter materials , e . g ., iodine - loaded mesoporous alumina , form the precursors of the glass - ceramic waste form of the invention . during the fixation process , one reduces the mobility of radioactive nuclides . for examples , one thereby induces : a ) phase change — gas phase iodine which adsorbs onto mesoporous alumina is transferred to ionic phase ( iodide , or iodate ); b ) part of the iodine being confined in the nanopores due to the encapsulation in nanopores , which is shown by the dramatic reduction of pore size and volume after the fixation ( see fig9 - 12 ); c ) reduction of solubility of the nuclide via changing the oxidative state , e . g ., rhenium ( re - vii ) to rhenium dioxide ( re - iv ). re is used as the surrogate of technetium in regular laboratory study ( see resulting waste forms of fig7 and 8 ). the fixation can be accomplished via metal complexation , reaction with alkaline metal hydroxide / salts , either in the form of solids or solutions , for example , sodium , potassium hydroxide and their silicates . the invention is also of a method of making cost - effective nanostructured glass - ceramic as the waste form for deposition . the principle is to make the waste form both durable and low cost . to reach this goal , htxrd ( high temperature x - ray diffraction ) is employed in parallel with leaching tests to optimize the vitrification condition for the most durable waste form . the combination result of htxrd ( fig4 ( a )) and leaching tests ( table 1 ) show the optimum vitrification temperature to be between about 800 to 900 degrees c . loading iodine on mesoporous alumina / composite . mesoporous alumina is weighed into a teflon jar , along with a vial which contains iodine weighed at the ratio of , preferably , about 1 : 10 ( i / mesoporous alumina ). the teflon jar is screw - capped and set in the oven at about 90 ° c . for 6 hours . then , the jar is opened in a hood and let cool to the room temperature . fixation of iodine loaded on alumina / composite . at about room temperature , about 3 g of iodine - loaded mesoporous alumina is ground - mixed with about 27 g of sodium silicate solution . the mixture is gradually dried at an increasing temperature from the room temperature to about 120 ° c . this dried mixture is referred to herein as the ‘ glass precursor ’. the glass precursor is then ground and mixed with frits ( e . g ., ferro co . according to table 1 ) or other glass forming components ( e . g ., silica ( sio 2 )). vitrification : the mixture is heated in air to a selected temperature between about 750 and 1100 ° c . depending on the composition and test conditions . leaching test : the resulting glass - ceramic waste form is ground and sieved to about 250 μm (& gt ; 90 %). about 0 . 8 to 1 gram of the ground material is set in about a 50 - ml buffer solution in a screw - capped plastic container , which is kept in a teflon jar with about 20 ml of di water . the screw - capped teflon jar is set in the oven for about 7 days at about 90 ° c . at the conclusion of each leaching test , the liquid suspension is filtered with filter paper . the filtrate is saved for further analyses . the residual leached glass is dried overnight and then subjected to edxrf analysis for iodine concentrations . these concentrations are then compared with the glass prior to the leaching test to determine the percentage of iodine loss from waste form during leaching . the filtrate is analyzed for its ph and silica concentration . iodine loading on mesoporous alumina composites . iodine loadings of the waste forms are given in table 2 . the adsorption capacity of the getter materials is shown in fig1 and table 3 . data in fig1 were obtained from exhaustion experiments , in which the iodine - loaded material was heated overnight at about 90 ° c . and cooled to about room temperature in an open jar . the data tabulated in table 3 are obtained from the sorption experiments without subsequent overnight desorption at about 90 ° c . note in table 3 that monolithic mesoporous alumina ( nc71 ) with no silver included exhibits higher iodine sorption capability than the material with silver , indicating that silver may not be necessary for iodine sorption . fixation of iodine with sodium silicate . during the fixation the form of the iodine in the mesoporous alumina is changed from gas to ionic species , as indicated by ftir spectra ( fig2 ). in fig2 , naoh - 12 stands for iodine which has reacted with sodium hydroxide solution . nc52 - 2 is the product of mesoporous aluminum - silver composite fixed with sodium silicate ( the glass precursor ). nc52 - 3 is an iodine loaded mesoporous aluminum - silver composite reacted with sodium hydroxide solution , with no silica involved . the spectrum labeled as ag — al — i stands for iodine - loaded mesoporous aluminum - silver composite ( before fixation by sodium silicate ). finally , the spectrum labeled as na 4 sio 4 is sodium silicate . all the compounds or materials analyzed are dried solids . the iodine in sample naoh — i 2 is expected to consist of iodide [ i (− 1 )) and iodate ( i (+ 5 )) forms due to the following reaction : although no detailed peak analysis has been performed , it is obvious that the spectra of naoh — i 2 and nc52 - 3 have overlaps around wavenumbers of 1440 and 790 cm − 1 , whereas , the spectrum of sample ag — al — i does not show any specific peak at these positions . therefore , the iodine form in initial mesoporous material is different from that in the fixed materials . because of this change of iodine into less volatile forms , the iodine loss during vitrification is minimal (˜ 0 %). leaching test . the final leachate solutions were subjected to silica concentration analysis ( hach silica method dr / 2400 ( 8185 ) for high concentration of 1 . 0 to 100 . 0 mg / l ). the dissolved silica concentrations , ph , and the loss of iodine during leaching are shown in table 1 . among the glass frits tested and other formulations tried , the frit 510 mixture resulted in the least iodine loss during leaching tests . frit 510 comprises 0 - 2 % al 2 o 3 , 12 - 15 % b 2 o 3 , 7 - 9 % li 2 o , 7 - 9 % na 2 o , and 68 - 72 % sio 2 . therefore , a preferred frit composition for encapsulation of iodine is recommended to be similar to that of frit 510 . the vitrification temperature can also affect waste form performance . the study shows that lower iodine loss due to leaching is observed for the waste form vitrified at lower temperatures in the range of about 750 to 900 ° c . microstructure analyses of glass - ceramic waste forms . a vitrification study using ferro frit “ 510 ” and iodine - loaded mesoporous alumina was conducted . the vitrification was carried out at temperatures of about 750 , 800 , 850 , and 900 ° c . for minutes , respectively . the resulting materials were characterized with xrd ( including htxrd ) and tem . fig3 ( a )- 3 ( d ) show the morphology of the ceramic / glass mixtures . the increasing surface exposure in terms of the void space due to bubbling during vitrification matches the durability decreasing with increase in temperature . the xrd patterns are shown in fig4 ( a ), which indicates the formation of li 2 si 2 o 5 mineral phase along with quartz , and cristobalite phase at 750 ° c . further heating results in loss of li 2 si 2 o 5 and slow disappearance of quartz and cristobalite phases . highly efficient mesoporous alumina and its composites are preferred as the getter materials ( adsorbents ) to sequestrate highly mobile radionuclides including 129 i . again , the present invention is of a method to convert these getter materials into durable waste forms at relatively lower vitrification temperatures ( and of the resulting waste forms ). the resulting waste forms are glass - ceramic nanocomposite that can immobilize a wide range of radionuclides with high loading capacity . ferro frit “ 510 ” with iodine - loaded mesoporous alumina is preferred for the formation of glass - ceramic waste forms based on the batch leaching tests , which indicated that this embodiment results in the least iodine loss during leaching tests . note that just for screening purpose ( to accelerate the experiments ) the leaching method used here involves rather aggressive physical and chemical conditions . unlike the conventional method for glass durability test ( using slab or cubic glass ), the waste form was ground to the size of 250 μm ( high exposed surface area ) and a weak alkaline buffer solution ( ph 8 . 5 ) was employed . for comparison , approximately the same temperature , duration , chemistry of initial solution , and size of the target materials were used for all leaching tests . the leaching rate of the waste form depends on the stability of both radionuclide - bearing nanocrytallites and their surround matrix . as shown in fig5 ( a )- 5 ( c ), iodine - bearing nanocrystals are embedded in an amorphous matrix . this is consistent with xrd analyses ( fig4 ( a ) and 6 ), which indicate that at a relatively low sintering temperature , e . g ., between 750 - 800 ° c ., several crystalline phases appear . the leaching test result indicates that glass - ceramic waste forms vitrified at 750 ° c . seem to have the lowest iodine loss during leaching . this may be due to the high content of crystalline quartz ( possibly as the embedding matrix ) as well as the presence of crystalline lithium silicate . actually , in the case that the glass ceramic sample containing ag , nanocrystals of agl are observed to be embedded in crystalline quartz . at a higher vitrification temperature , iodine anions are expected to distribute more uniformly in the resulting waste form , probably “ dissolved ” in glass matrix , high silica leaching rate for the lower temperature waste forms is directly related to the resulting solution ph . in these waste forms , na is not completely incorporated into al — si — o frameworks . the preferential release of na gives rise to the high solution ph . for waste species other than iodine , such as technetium , it is anticipated that during the fixation process of the invention an oxyanionic species such as tco 4 − may also change its oxidative status to a less soluble reduced form , e . g ., from tc ( vii ) o 4 − to tc ( iv ) o 2 . nanopore structures in an adsorbent play important role in radionuclide sequestration and encapsulation . as shown in table 4 , the presence of nanopores in the initial adsorbent material reduces iodine losses in subsequent fixation and vitrification processes . to conclude , the present invention is of a method for the formation of nanostructured glass - ceramic waste forms that can be used for disposition of various radionuclides , especially iodine . this method is based on use of , preferably , mesoporous alumina and its derivatives as getter materials for entrapping gaseous iodine . in this method , iodine sorbed on mesoporous material is first reacted with sodium silicate to convert molecular iodine into less volatile ionic species . the resulting material is then vitrified with additional glass - forming components so that iodine forms nanometer precipitates that are encapsulated in either a glass or a crystalline matrix . the loss of iodine during vitrification is minimal (˜ 0 %). the preferred vitrification temperature range ( 850 - 950 ° c .) has been determined for the least iodine loss during a waste form leaching test . this temperature is lower than that generally used for glass formation . specifically , the method reported here does not require using silver for immobilizing iodine , thus reducing the cost of waste form development . note that in the specification and claims , “ about ” or “ approximately ” means within ten percent ( 10 %) of the numerical amount cited . although the invention has been described in detail with particular reference to these preferred embodiments , other embodiments can achieve the same results . variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents . the entire disclosures of all references , applications , patents , and publications cited above are hereby incorporated by reference .
a waste form for and a method of rendering hazardous materials less dangerous is disclosed that includes fixing the hazardous material in nanopores of a nanoporous material , reacting the trapped hazardous material to render it less volatile / soluble , and vitrifying the nanoporous material containing the less volatile / soluble hazardous material .