DE1496676A1 - Composite glass bodies, especially for radioactive substances, as well as the method and device for its production - Google Patents

Description

DIPL-ING. ERICH SCHUBERT

- Telephone number 22802

Telegram addr .: Palschub, Siegen

Abs .: Patent attorney Dipl.-lng. SCHUBERT, 59 Siegen (Wostf.), Postfach325 Posticheckkonten: OronienstrgBe 14 ■ 'ι ■ ι - »- ι— ^ Cologne 106931, Essen 203S2

Dr. Expl.

Sj 246 ür.Bü / soh.i _IJf . ■ _v , » _{a DeuhcheBonk} ag ..

Bank accounts: Deutsche Ban branches Siegen and Oberhausen (RhId.)

August 8, 19o'j

• 11. μ,: ..iüV ". Α'ϊϋΚΙϋ -wii ±] RGi ΑϋϊηΟΗΙΐί, Patenta Brancn, 11 -12, Jiibirles II otreet, L ο η d ο η, S. tf.1, England

Me this filing will take priority out of the UK

• r-

Patent application Iir ", 30847/62 from August 10, 19-62 üeanapriicnt"

Verbund-ΰ-1 agkorper, especially for radioactive substances, as well as method and device for its creation

The invention relates to a new composition V021 Materie / new composition of matτer /, in particular on a radioactive one Composition by Liaterie, and on a new Hers Gegans'; and, which contains this composition.

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BAOORlGtNAL

According to the invention, an ICoiiieoaition of Later ie. (Yerbüiid-G ^ aslcbody) created ·, which consists of an i-eschioi glass body / fused glass / with a ^ melting point in aer order of magnitude of 350 - 11 Ou ⁰ U ueate.it or him aux \ / c: iet and in the v / esexitliclien from glass-forming ^ ox; the il.ü voii 2ü - 50 percent by weight from aofalloxydeu - as later ue _. \ :. is not - is exhausted »

The expression "melting point" has become known lic η keiue ecnce Meaning in x ^ eziug on Glaser; the approximate values indicated below therefore refer to 'U- those!' eiu in which an i ^ essential blaae ^ free oorjuelze obtained we α.

The expression ".-Vufallox ^ de" / "..aste oxides ",;", as it ends above, is intended to denote a 'J-emic of oxides present in the waste or effluent .de; i ai..i, di3 uei uer jbelii..iidlun._: for the V / iedergewinnune, irradiated from ^ r ^ n and PlutOni'jj-i en ^ ietallischexfi üran-ivernbrei-u'xstofrJ ait one Bronn time of more than 300 MM / t occur, such Aüfdloxyde consist of oxides of op alt pro ά. "-: ie ;: uit einii. low content of ^TT ranoxyd and oxides, of the j-iegierungszuschla eön-derived, which are added to the uranium AUON oxides, aie the ITmhUllungamaterial entstamaien, köijien present Ain. These waste oxides are liormally in the expiring

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BAD ORIQiNAL

Solutions “Is itrajie found, and therefore - ^ e ^ Usages to _bf allox, yde in the i-: achf oil renaen are to be interpreted in such a way, dan ar.o;" ^1. They include solutions of the corresponding rate.

Ivi ei.! ...., typiöcner ü'all köimen Zufallox ^ de mainly composed of ueii i'ulgisnuen elements ^ a:

i3arxum 28 Certainly Oer 67 Caesivjii 60 Lanxhaii 30th IuO Iy Ό dan 78 lieodyn 97 iPalladluifa 17th Prase od .. u 3ü HhodiuiiL 12th I'iutheni / iU 45 'oaiaariuiii 16 btroiititUii 22nd Teclinetiuni 20th Tellurium 10 f tr ruin 11 Zircon 89 iron HO Aliiiiiniura 180 L ^T ran 90 3Yat Il II Il It Il M. H Il Il Il Il I! Il Il Il Il Ii Il

.ds can probably also lie smaller ones f oil - = i'.aen elements be present:

909828/06 53 ORIGINAL BATHROOM

Silver • tiu.ro ρ ium Promethium Rubidium Chromium

Wrap Liagriesium Silicon

The exact ratio of these elements in the oxyden varies depending on many factors.

-L> he glass-forming oxides can be selected from the following oxides:

Calcium. ·

boron

Sodium - · ■

Phosphorus silicon lead

molybdenum

Zinc -

Aluminum biscuits

Bs should be noted that boron, phosphorus and silicon each in the form of borates, phosphates and ^above ilikaten may be present "

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According to the invention, the new composition by Liaterie is in the form of a completely fused glass and is preferably contained or embedded in a vessel made of steel. As a result, the present invention can also be used as a fabrication device, an item of manufacture, and an item of manufacture which contains the new composition of katerie - as defined above - and which are in situ or in place is formed or molded into this ^ vessel.

The invention is then used as a new subject matter a radiation source ^ eschaff e.u, which im -, ve sent lic heu ■ hoiiio.gei.1 and which has a relatively long xialbwertzeit, resulting from the well-known long half-lives of the radioactive oxides which form the waste oxides the formation of the glass according to the invention may be more advantageous postpone or delay until the waste oxides have an opportunity to age or mature for a period of time have had bia five years near their removal from the Heater to prevent the fission products from heating up, unless this is expressly desired, whereby a mixed Spectrum of gamma rays is delivered, which in the is essentially free of beta rays or alpha particles, and since the steel vessel is normally closed, it is also "

.-. "" "becomes ,, The new article of manufacture can be used as a source of steel V used. ■

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BATH ORIGINAL

the dtralilun ;; scmelle normally be free from any / he seuahun. ^ s danger. In this JusazMiei- ^ szig aei-auf

df

pointed out / generally u-lae-compositions resistant to .auslaugung are so dau> selost in ae ^ i uri./axirscheiiilichen J ¹ ~ li of leaks in the oxalilgef-iöea no merkbares Entweioiien radioactive ^ ^ ls ateri au expect üz / w. to be feared iyt. In any case, the radioactive decay process will cause self-heating in the new obstruction, which can be used for a relatively long period of time if the heating effect decays less than the radioactive effect .

Finally it is of enbc., R, that the Srfi ^ dun ^ Lit v el for the ßese it idling der. ^ Bfalloxyde: απ die nand gio " ^: * '> insofar as this is in the new i ^1. , BriiCationagegi, nsttjriä ain, jeweled and therefore be accommodated on this ie3 \ ggnete 7 / ei3e, without there being a noticeable risk for the spread of radioactive 7e3? seuchim £: ·

It should be noted that jlliser, the abial oxides contain resulting from the iiiifarbeitting of fuels with relatively low burning time or the processing of non-metallic fuels, generally outside are within the scope of the present invention. At present it is impossible to say what kind of waste

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oxy de from processing rLioh-t-metallisalier .Fuels his werueii and whether it will be possible, this in an inventive To incorporate G-las.

make the present invention more understandable should mm the procedure for the preparation of the new Product of manufacture using an example and with reference to the schematic drawing, which shows a work plan is to be described in more detail.

The new fabrication object in this embodiment consists of a stainless steel cylinder 1 with 6 inches (15.2 cm) inside diameter and 5 U ¹ US (152 cm) length, this cylinder being partially filled with the molten glass composition in due course. Once this has been done, the device 1 is inserted into an oven 2 which has six independently controllable heating elements and whose holder 3 (for oven 2) is set up so that the oven can be raised and lowered in relation to the cylinder . The upper end of the cylinder is provided with two lines 4 and 5 which are connected by couplings to an inlet pipe 6 and a grass discharge pipe 7, respectively. A solution of the waste oxides and a slurry of the glass-forming oxides, both conveniently in nitric acid, are mixed together and the resulting slurry is through line 6 into the

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Cylinder 1 fed in, - the furnace heating elements are adjusted so that the paste is heated to such an extent that the water content is driven off and the nitrates decompose into oxides, although initially in the bottom part of cylinder 1 there is a feuc'ate sintered mass forms. Meanwhile sch with the progression of time and the Hot If the cylinder, these sintered mass bucket molten glass that fills the lower part of the cylinder. When a sufficient amount of glass has formed in the cylinder, the furnace 2 is brought up in relation to the cylinder 1 and brought to a maximum temperature of 1100 °, so that the remaining sinter or sintered body and also the Splashing into the upper part of the cylinder melt precipitated dust.

It is obvious that it is through the gas pipe flowing gas is contaminated by oxide mist or oxide, and it is of the utmost importance to keep the temperature of this gas low enough to allow it to combine Oxydnebels or -statrbs and thus a blockage of the To prevent conduction. For this reason a lower one had to be Limitation of the melting point range of the glass because there must be enough room for the gas cooling to prevent sintering in the pipes to prevent. Similarly, there had to be an upper limit

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.-.- ■ '■ BAD'ORIGINAL

of the melting range are named because ordinary and stainless steels are not used much above 1100 ⁰ O - .. earth kÖiaien, auiiial a sufficient security factor for possible defects in the vessel must be taken into account and it must be remembered that what is formed in the vessel Glass is radioactive »

Jie Gaaabxührungsleitung 7 is connected by a suitable coupling to the conduit 5a of a same cylinder 1a in.einem separate furnace is untergeuracht 8, wherein the furnace is adjusted so that it maintains the temperature of the cylinder 1a atif 25O ⁰ Q. The cylinder la houses a Primur filter element 9 »■ '" which has the task of extracting ruthenium, which is volatile from the oxides of the oxides, and this filter can conventionally be extracted from iron oxide in a perforated hollow container - exist, xiieoes filter is mounted in such a way that it closes the line 4a by means of a .se ame! ζ bar en ^ i ^ iitveroindiui-isstüokes 11, which is located in a Ufen at 250 ⁰ G and which contains a large Seloindär-Mlter-Slemeiit 13. The exhaust gases passing through the filter 13 are passed into a condenser 14, in which the water is separated off, and then pass through a rose absorber tower 15, which is fed with the condensate from the condenser 1.4, with nitric acid as a by-product to win.

90 $ 828/0653

The gases from the absorber 15 go through an ALcali wash 16, a filter 17 and a vacuum ejector 18, before they are blown into the atmosphere. The ejector 18 serves to maintain a slight negative pressure outside the apparatus upright ziier shark part.

When the cylinder 1 is filled with glass to the level one "cand, the pulp flow is removed and the furnace - as already mentioned - is lifted onto the cylinder in order to remove any remaining sinter in the cylinder Schmelzer *. The cylinder is then cooled, from the extensively removed eagle owl forms the new object of communication. At the same time , the cylinder 1-a-is cooled and filled in 2, while a new cylinder is in the furnace 8 is inserted, - / irά. jjei the increase in the temperature of furnace 2 to the original temperature, the Zi carrying the filter 9 melts at around 42U ⁰ G _11, whereby the temperature in the Jodeii of the Zy.xi

where it is enclosed in the 'j-las forming in the cylinder will."

In the event that a phosphate glass composition is used, as already described, some corrosion of the cylinder material may occur and it is therefore desirable to protect the inner surface of the cylinder. This can be done by atomizing aluminum on ^: the inner surface of the cylinder with subsequent oxidation

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this aluminum and by adding iiltmiiuixua to the Glass oi position up to an ubeidOhuss of 20 percent by weight happen. ..aiiiweise the glass can also contain amounts of iron up to 20 weight percent can be added.

Glass compositions that meet the new requirements katerie- ^ omposition should now im described individually. Bs should be mentioned that the majority of these glass-forming systems are three-component systems are and that a number of compositions in more satisfactory v / ice glasses result which melt in the range described above. For this reason, those listed below Compositions maximum lack of each of the constituents the composition, and also for each composition special lihe has been devoted to it. the most satisfactory Pointing out the top composition. -Uie top accessories There must of course be a compromise between the ease of glass formation on the one hand and the vifidei'stand as opposed to being leached, the easiest to leach On the other hand, be constituents. Where it was possible are the glasses have therefore been tested for their resistance to leaching, and the leaching factors are sodium, potassium and oalcium been specified (where this "bestimiut vmrden") to specific Examples outside the wide range of possibilities

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BATH ORIGINAL

admit. Care must be taken to ensure that the glass additives are used are specified to be between 20 and 50 Contain weight percent of the waste oxides, wouei the lower Limit is determined by the fact that below this an insufficient Lienge of waste oxides contained in the jar, and the upper limit due to the tendency to instability of the Glasses with too high a content of waste oxides The preferred one The content of waste oxides is between 3o and 40 percent by weight.

In the following tables for glasses are all compositions given in percent by weight, the temperatures in degrees Celsius and the leaching factors in Arbitrary units, with a high value being a glass with high leach resistance. A leach factor of 1 means the lower limit of usability, a Falccor of 10 is sufficient and a factor of 100 is highly desirable.

Finally mula also mentions "that those below experiments described were carried out on simulated (non-radioactive) or diluted / spiked / waste oxides, "Weilbis now there was not a sufficient quantity of true waste oxides available, and in some cases potassium was used for cesium and bubidium became. . -

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BATH ORIGINAL

"3e-iapiel I.

Mepheline Syerit-Galeiumoxyd-IJoraäureanhydrid-Systeiii »

. Mephelin syenite is a feldspar, which has the advantage, under acidic conditions, a gel to "form which is easy and olme Spitting dried Br melts at about 1.225 ⁰ G ₁ and its approximate composition in percent by weight is:

Silica 60 Clay 24 Sodium oxide 10 Potassium oxide 5 Magnesia J. 1

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Z-usaniLiensetaung Hepheline
Syenite Oaloium
oxide , 7 Boron-
oxide Enamel
Point Lying factors 10 10 AMaIl-
oxides 11 "13.3 'C iJatriu.a üalium Uale ium 10 10 22nd 23.4 <$ 9 ,8th 15.6 1050 10 1ϋ 22nd 23.6 7th , 9 Qe, β 10CO 22nd 50.9 3 , 4 23.2 1000 10 ' 10 22nd 39 23 , 6 15.6 1000 10 22nd 54.6 17th , -> 5.8 root 10 10 22nd ^ 38.5 10 21 1050 10 30th 25th Φ 20th 1050 30th 21 14th 35 1000 10 30th 18th Td ΡΔ
4P
i 10CG 4 ο
40 ^ o

Example II
iiatrium phosphate-potassium oxide-meselic acid-sysxoite,

In this system, the "better glasses" are the ones Have a low oalcium content.

ADDITIONAL SUPPLY Pliosphi.t C al c ium- £ ± donkey · · acid gunSf ^lzJ Leaching factors 100 40 Waste sodium ^ 4 oxide 6th β Λ- * iatrium. Potassium tJalciuja oxides 39. O 4i C. 40 51 0 0 900 40 42 4th 12th 950 40 42 6th 18th 900 40 0 950 - 40 950

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SAO

Example III

Encouragement Lead-" Borsre- pebble Schnielz
jpimkt Leaching factors waste oxide anhydr. acid Sodium Potassium Ualοium oxides £ 64 8th 8th .20 32 8th <40 1000 20th 48 <32 ü 1050 20th 43 16 16 950 20th ^ 49 14th ■ 7 950 6th 30th 28 14th ^ 28 1000 30th 35 4 ^ 28 7th 1000 1 30th 950

Example IY Iiatrium phosphate-lead oxide-boric acid system.

In this system there are only (iläs with Solanielz points

vO

been considered under about 950 ö "

composition liatrium
phosphate lead
oxide Borsre-
anhydride Melting '
Point Leaching factors Potassium 0 aleium JUDfall-
oxides ^ 60
6th
48
36 0
<^ o
6th
12th 0
■ <* ♦
6th
12th Hatrium 20th
20th 40
40
40
4o 850
950
900
• 900 , 5
20th
• 50

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Example Y ".

Sodium phosphate-lead oxide-silica system.

. In this system only glasses ^{melting below Mb about 95O 0} G are considered. The presence of lead does not seem to affect the leaching factor, but it does slightly increase the mobility of the melts.

Composition sodium
phosphate lead
oxide pebble
acid Enamel
Point Leaching factors 10 waste
oxides ^ 57 0 3 Sodium potassium calcium 10 40 3 0 goo 40 42 3 900 40 48 ο. <Ί2 900 40 54 0 6th 950 60 40 900 80

Example VI ,

Sodium phosphate-sodium silicate systems.

In this system only glasses that are below about 95o ° G Melting, considered. The system has the advantage of being contains no boron and the glass-forming additives are completely soluble are. ■

Composition Enamel
Point Leaching factors Waste Sodium Sodium
oxides phosphate silicate Sodium potassium calcium 50 ^ 50 0
30 £ 70 0
20/70 10
30 40/30
40 ■ 55 5 CD VD CD CD VD
VJl VJl VJl VJl VJ)
O O O O O 10. 10

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BAD ORIOfNAL

Example VII

Borophosphate-Sodium Oxide-Silicic Acid Syöte.ii] ..

In this system only glasses that are below about 95o ^Q (J üchiaelaen,

Zu3 anihiens et tion

Leaching factors

Waste boron, sodium, silica, phosphate oxide

jtfatrluin potassium calcium

40 <42 40 30th 40 27

12th

6 6

15th

Example VIII

iiatriuiaphosphate-lead oxide-zinc oxide system.

In this system only grass lasers that maintain about 95O ⁰ C schmelaexi, "are considered. ■

Addition Hasatrium , 5 Lead- 5 £ ink- Melting Leaching factors ■ phosphate ogrd 5 oxide punlcb waste 4 * 5 5 0 7th Fat potassium oxides / 63 > ⁵ » 5.5 30th 38 <24, . ■ 7 850 30th 49 7th C21 900 50 45, 21 Φ.5 950 30th 42 900 30th 900 30th §00 10

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BATH ORIGINAL

Example IX . .
Liatric oxide-silica-calcium oxide-boron oxide system.

The G-I as composition contains a fixed ratio from sodium oxide to silica.

Composition <9.1
5.6 <56.4
22.4 14th 1o, 5
14th Enamel
Point Laugungs factors 4th Calcium 4.9 19.5 7th 58.5 Sodium potassium 8.4 55.6 1o, 5 17.5 1000
950 Waste I Sodium Silica Oalcium Boron
oxide oxide acid oxide oxide 950 5 50
50 1000 4th 50 50

Example X

Borax silica system.

A typical glass of this system contains 40 fo al oxides, 40 io borax and 20 fo silicic acid. It melts at approximately 95O ⁰ C and has a leaching factor of about 0.2 for liatrium. This system was used to form a radioactive glass that gave Gurie units of the same height as Eu ^ or Pr. The glasses obtained had reasonably adequate leaching characteristics only with low proportions of waste oxides.

■ Example XI '

Molybdenum Trioxide Potassium Phosphate Syst em.

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Glasses in this system, the 30 fo Abfalloxyde and contained up fo up to 40 molybdenum trioxide were tested and found with a "melting point below 95O ⁰ G" MEIE these glasses were slightly soluble in water and dilute mineral acids.

Example XII

Matium phosphate-silica-lead oxide-iron oxide system.

This glass was developed from the system in the example V, with the .ülisenoxid (iVepO.,) Was added to the corrosion to reduce the steel container by the phosphate-containing glass.

composition phosphate oxide pebble Iron egg Enamel leaching sf act or Abf ε.11-sodium-lead 53 MM acid oxide Point Ifatrium oxides 47.7 5.3 _H _ 7.0 850 40.0 42.4 10.6 __ 7 ^ 0 870 23 40 42.4 7.95 __ ■■ 7.0 900 40 39.75 7.95 2.65 7.0 880 40 39.75 5.3 5.3 7.0 880 40 42.4 7.95 7.0 880 40 47.7 __ 10.6 7.0 870 40 45.05 5.3 5.3 7.0 850 100 40 42.4 5.3 2.65 7.0 860 14th 40 45.05 2.65 5.3 7.0 870 110 40 5.3 7.0 860 84 40

The invention also relates to modifications of the embodiment outlined in the accompanying patent claim 1 and relates above all on all features of the invention that individually - or in combination - in the entire original Application documents are disclosed, '"

claims 909828/0653

ÖAO ORIGINAL

Claims (1)

PATENT ADVOCATE. DIPL-ING. ERICH SCHUBERT $ 0 Phone: 22802 Telegram address: Patschub, Siegen Abs .: Patent attorney Dipl.-Ing. SCHUBERT, S) Siegen (Westf.j, Poitfadi 325. Posticbeakonten: OronienslraBe U ' KOIn 1069 31, Eisen 203 Ά 63 24-β Dr. J Jü / SG lim bank accounts: / QC ß 7 R Deutsche Bonk AG., Branch · »» Siegen and Oberhausen (RhId.) 6. Au / raat 19o3 Pat ent ans orr.olie 1. Composition · ν \ · η i.iaterle, daduioh jekennzeich.net, daJ.3 it consists of a molten iilas iait aui οαηάβΙζρΐύύΛ ± ii area, from & jö to 11Gü ⁽ "'j. And Iu essential cxia glabbildenden oxides and from 20 to 50 percent by weight of waste oxides, as defined herein, is composed. 2. Matter composition according to claim 1, characterized in that that the glass-forming oxides from the oxides of calcium, Bors, UTatriums, i ^ hosphors, Siliciums, -lileis, Liolybdäi.s, Zinlcs, Aluuiiiiums and iron selected'v / earth * 3. Liaterie-iComposition according to claim 2, daauron characterized in that .jor, hiosphorus or silicon: in -e'orm of their borates, Phosphates or liilLcate are verv / ends. 4. iuaterie composition according to one of claims T - 3, characterized in that the composition is 30 - 40 percent by weight Waste contains. - BAD ORlOiNAL 909828/06 53 5.- Glass melt, characterized in that it is 42.4 "to 47.7 percent by weight sodium phosphate, 0 Ms 5.3 Percentage by weight of iron oxide, 0 to 5.3 percent by weight of lead oxide, 7.0 percent by weight of enoxyd iurd. 30 to 40 percent by weight Contains waste oxides. 6. Articles of trade, in that it indicates that it is a Mass of molten ία glass according to any one of claims 1-5, this glass being formed in a steel-like vessel Y / ircl and it contains » 7 ο procedures for the disposal of radioactive waste oxides, characterized in that the waste oxides in A molten glass batch as claimed in any one of the claims 1-5 can be deformed into it, with diose glass in one st-ahlhaltivjem vessel is formed and this vessel is then closed willo BATH 909 828/06 5 3 Le first page