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The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes

Conference:

Abstract

One of the features of the hot-atom reactions obtained as a result of nuclear transformations is that labelled polymeric products can be formed. This tendency is very marked in the case of polyvalent recoil atoms, where the polymer yield can, in certain cases, reach an amount of about 90% of the total activity. The aim of the present research is a study of the behaviour of recoil atoms of sulphur-35 and carbon-14, obtained in the nuclear reactions Cl{sup 35}(n, p)S{sup 35} and N{sup 14}(n, p) C{sup 14} in gas and liquid phases. It can be assumed that in the stabilization process hot carbon atoms form methylene biradicals, whose behaviour, by reason of their reaction capacity, greatly resembles that of atomic sulphur. The investigations were conducted like those for paraffins (CH{sub 4}, C{sub 2}H{sub 6} ), and for cyclic hydrocarbons (cyclohexane, cyclohexene, benzene). The binary systems comprising hydrocarbons on the one hand and S{sup 35} and C{sup 14} hot-atom donors on the other were subjected to irradiation. Compounds of CCI{sub 4}, HCl and ammonia were used as the donors. Irradiation was carried out on a reactor of type IRT-1000 with a thermal neutron flux of 10{sup 11}-10{sup 12} n/cm{sup 2}. s.  More>>
Authors:
Dzantiev, B. G.; Stukan, R. A.; Shvedchikov, A. P.; Shishkov, A. V. [1] 
  1. Institut Himicheskoj Fiziki AN SSSR, Moskva, SSSR (Russian Federation)
Publication Date:
Apr 15, 1965
Product Type:
Conference
Report Number:
IAEA-SM-57/60
Resource Relation:
Conference: Symposium on Chemical Effects Associated with Nuclear Reactions and Radioactive Transformations, Vienna (Austria), 7-11 Dec 1964; Other Information: 17 refs., 2 figs., 2 tabs.; Related Information: In: Chemical Effects of Nuclear Transformations Vol. I. Proceedings of the Symposium on Chemical Effects Associated with Nuclear Reactions and Radioactive Transformations| 457 p.
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY AND NUCLEAR CHEMISTRY; CARBON 14; CARBON TETRACHLORIDE; CHLORINE 35 REACTIONS; ETHYLENE; HOT ATOM CHEMISTRY; IRT REACTOR; NEUTRON REACTIONS; NITROGEN 14 REACTIONS; PARAFFIN; POLYMERS; PROTONS; RADIATION EFFECTS; RECOILS; SULFUR 35; SYNTHESIS
OSTI ID:
22141782
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); Joint Commission on Applied Radioactivity of the International Council of Scientific Unions, Paris (France)
Country of Origin:
IAEA
Language:
Russian
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M3312096383
Submitting Site:
INIS
Size:
page(s) 399-407
Announcement Date:
Oct 24, 2013

Conference:

Citation Formats

Dzantiev, B. G., Stukan, R. A., Shvedchikov, A. P., and Shishkov, A. V. The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes. IAEA: N. p., 1965. Web.
Dzantiev, B. G., Stukan, R. A., Shvedchikov, A. P., & Shishkov, A. V. The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes. IAEA.
Dzantiev, B. G., Stukan, R. A., Shvedchikov, A. P., and Shishkov, A. V. 1965. "The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes." IAEA.
@misc{etde_22141782,
title = {The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes}
author = {Dzantiev, B. G., Stukan, R. A., Shvedchikov, A. P., and Shishkov, A. V.}
abstractNote = {One of the features of the hot-atom reactions obtained as a result of nuclear transformations is that labelled polymeric products can be formed. This tendency is very marked in the case of polyvalent recoil atoms, where the polymer yield can, in certain cases, reach an amount of about 90% of the total activity. The aim of the present research is a study of the behaviour of recoil atoms of sulphur-35 and carbon-14, obtained in the nuclear reactions Cl{sup 35}(n, p)S{sup 35} and N{sup 14}(n, p) C{sup 14} in gas and liquid phases. It can be assumed that in the stabilization process hot carbon atoms form methylene biradicals, whose behaviour, by reason of their reaction capacity, greatly resembles that of atomic sulphur. The investigations were conducted like those for paraffins (CH{sub 4}, C{sub 2}H{sub 6} ), and for cyclic hydrocarbons (cyclohexane, cyclohexene, benzene). The binary systems comprising hydrocarbons on the one hand and S{sup 35} and C{sup 14} hot-atom donors on the other were subjected to irradiation. Compounds of CCI{sub 4}, HCl and ammonia were used as the donors. Irradiation was carried out on a reactor of type IRT-1000 with a thermal neutron flux of 10{sup 11}-10{sup 12} n/cm{sup 2}. s. It is shown that for various compounds in the liquid phase, up to 60-90% of the sulphur-35 becomes stabilized in the form of a polymer, the yield of which is highly dependent on the composition, passing through the maximum at a nearly equimolecular ratio of components. In the gas phase the polymer yield amounts to 30-40% of the total activity. By means of paper radiochromatography it was established that labelled polymer products have a complex structure and are, at the least, a mixture of compounds of two qualitatively different types whose yield changes in various ways depending upon the ratio of the components. An increase in irradiation time leads to an increase in the labelled polymer yield. In the case of the liquid phase system C{sub 6}H{sub 12}-CCl{sub 4}, the molecular weight of the polymer was determined by capillary diffusion and found to be 5000 for the polymer of one type and 500-1000 for the other. The formation of a labelled product with a high boiling point was also observed when pure CCI{sub 4} was irradiated. Analogous experiments were carried out in an ethylene-ammonia system in the gas phase, at high pressure. It is shown that in this case, when pure anhydrous ammonia is irradiated the basic labelled product is C{sup 14}H{sub 4}. However, when even small additions of ethylene are made, a considerable proportion (up to 80%) of C{sup 14} becomes stabilized in the form of a polymer, whose yield also varies extremely with the growth in the proportion of ethylene in the system, attaining a maximum when there is 10-15% of C{sub 2}H{sub 4}. It is shown that if C{sup 14} polymer yield is plotted against composition, the shape of the curve does not change when dose rate and flux are increased. (author) [French] Les reactions que provoquent des atomes chauds obtenus a la suite de transformations nucleaires presentent la particularite de donner lieu a la formation de polymeres marques. Cette tendance est particulierement nette dans le cas des atomes de recul polyvalents ou le rendement en polymere peut parfois atteindre un ordre de grandeur approchant 90% de l'activite globale. Le memoire a pour objet d'etudier la formation de polymeres marques lors de la stabilisation chimique des atomes {sup 35}S et {sup 14}C de recul obtenus au cours des processus {sup 35}Cl(n, p){sup 35}S et {sup 14}N(n, p) {sup 14}C en phase gazeuse et en phase liquide. On peut admettre que pendant la stabilisation les atomes chauds de carbone provoquent la formation de radicaux doubles de methylene dont la reactivite rappelle beaucoup le comportement du soufre atomique. Les etudes ont porte tant sur les hydrocarbures satures (CH{sub 4}, C{sub 2}H{sub 6}) que sur les hydrocarbures cycliques (cyclohexane, cyclohexene, benzol). On a irradie des systemes binaires hydrocarbure-substance generatrice d'atomes {sup 35}S ou {sup 14}C chauds. Comme substance generatrice d'atomes chauds, on a utilise CCl{sub 4}, HCI et NH{sub 3}. L'irradiation a ete faite a l'interieur d'un reacteur du type IRT-1000, dans un flux de neutrons thermiques de 10{sup 11} a 10{sup 12} n/cm{sup 2} * s. Les auteurs montrent que pour differents hydrocarbures en phase liquide 60 a 90% de {sup 35}S se stabilisent sous la forme d'un polymere dont le rendement depend, dans les cas limites, de la composition du systeme et passe par un maximum lorsque le rapport moleculaire des composants du systeme approche de l'unite. En phase gazeuse, le rendement en polymere represente 30 a 40% de l'activite globale. Par radiochromatographie sur papier, on a etabli que les polymeres marques sont d'une constitution complexe; il s'agit d'un melange de deux composes de types qualitativement distincts et le rendement en ces deux composes varie differemment et depend du rapport des composants du systeme. En augmentant la duree d'irradiation, on active la formation du polymere marque. Pour le systeme C{sub 6}H{sub 12}-CCl{sub 4} on a fait appel a la methode de diffusion par tube capillaire pour determiner le poids moleculaire du polymere contenant {sup 35}S, qui est de 5000 pour l'un des polymeres et de 500 a 1000 pour l'autre. On a constate qu'un produit marque a point d'ebullition eleve se formait egalement lorsqu'on irradiait du CCl{sub 4} a l'etat pur. Des experiences analogues ont ete faites sur le systeme ethylene-ammoniac en phase gazeuse sous haute pression. Les auteurs montrent que lors de l'irradiation d'ammoniac seul, le principal produit marque est {sup 14}CH{sub 4}. Cependant, il suffit d'ajouter de petites quantites d'ethylene pour qu'une fraction importante (jusqu'a 80%) de {sup 14}C se stabilise sous la forme d'un polymere dont le rendement varie egalement, dans les cas limites, en fonction de la teneur du systeme en ethylene, en atteignant un maximum lorsque cette teneur est de 10 a 15%. On constate que la forme de la courbe qui exprime le rendement en polymere marque par {sup 14}C en fonction de la composition du systeme ne subit aucune modification lorsqu'on augmente l'intensite de la dose et du flux. (author) [Spanish] Una de las caracteristicas de las reacciones de atomos calientes, obtenidoscomo resultado de las transformaciones nucleares, es su capacidad de formar polimeros marcados. Esta tendencia es especialmente acusada en el caso de los atomos de retroceso polivalentes, en el que el rendimiento del polimero suele alcanzar un valor del orden del 90% de la actividad total. Los autores investigaron la formacion de productos polimerizados marcados durante el proceso de estabilizacion quimica de los atomos de retroceso azufre-35 y carbono-14, obtenidos en las reacciones nucleares respectivas {sup 35}Cl(n, p){sup 35}S y {sup 14}N(n, p) {sup 14}C en fase gaseosa y liquida. Puede suponerse que en el procesodeestabili- zacion los atomos calientes del carbono originan la formacion de birradicales metilenicos que, por su capacidad de reaccion, tienen un comportamiento muy parecido al del azufre atomico. Las investigaciones se efectuaron con hidrocarburos parafinicos (CH{sub 4}, C{sub 2}H{sub 6}) y ciclicos (ciclohexano, ciclohexeno, benceno). Irradiaron sistemas binarios compuestos por el hidrocarburo, por una parte, y por dadores de atomos calientes del {sup 35}F y del {sup 14}C, por la otra. En calidad de dadores se utilizaron compuestos de CCl{sub 4}, HCl y amoniaco. La irradiacion se efectuo en un reactor de tipo IRT-1000, con un flujo de 10{sup 11} a 10{sup 12} neutrones termicos/cm{sup 2} * s. Los autores demuestran que para diversos compuestos en fase liquida, del 60 al 90% del azufre-35 se estabiliza en forma de polimero, cuyo rendimiento depende de la composicion, pasando por un maximo cuando la relacion entre los componentes tiende a ser equimolecular. En fase gaseosa el rendimiento del polimero representa del 30 al 40% de la actividad total. Por radiocromatografia sobre papel establecieron que los polimeros marcados poseeh una composicion compleja y constituyen una mezcla de por lo menos dos tipos de compuestos cualitativamente diferentes, cuyo rendimiento varia de distinta manera en funcion de la relacion entre los componentes. Un aumento del tiempo de irradiacion se traduce en un mayor rendimiento del polimero marcado. Para el sistema C{sub 6}H{sub 12}-CCl{sub 4} en fase liquida, el peso molecular del polimero se determino por difusion capilar, hallandose valores de 5 000 para el polimero de un tipo y de 500 a 1000 para el otro. Se observo tambien la formacion de un producto marcado de elevado punto de ebullicion al irradiar el CCl{sub 4} puro. Se efectuaron experimentos analogos en un sistema etileno-amoniaco en fase gaseosa a elevada presion, demostrandose que en este caso al irradiar el amoniaco anhidro puro, el principal producto marcado es el {sup 14}CH{sub 4}. Sin embargo, la adicion de pequenas cantidades de etileno hace que una gran parte -hasta el 80% - del {sup 14}C se estabilice en forma de polimero, cuyo rendimiento tambien varia considerablemente al aumentar la proporcion de etileno en el sistema, alcanzando un maximo cuando esta proporcion es del 10 al 15% de C{sub 2}H{sub 4}. Los autores demuestran que cuando el rendimiento del polimero marcado con {sup 14}C se representa en funcion de la composicion, la forma de la curva obtenida no se modifica al aumentar la intensidad de dosis y el flujo neuttonico. (author) [Russian] Odnoj iz osobennostej reakcij gorjachih atomov, poluchajushhihsja v rezul'tate jadernyh prevrashhenij, javljaetsja sposobnost' k obrazovaniju mechenyh polimernyh produktov. Naibolee jarko jeta tendencija projavljaetsja v sluchae polivalentnyh atomov otdachi, prichem vyhod polimera mozhet dostigat' v otdel'nyh sluchajah velichiny porjadka 90% ot obshhej aktivnosti. Cel'ju nastojashhej raboty javljaetsja issledovanie obrazovanija mechenyh polimernyh produktov v processe himicheskoj stabilizacii atomov otdachi sery-35 i ugleroda-14, poluchajushhihsja po jadernym reakcijam Cl{sup 35} /n, p/S{sup 35} i N{sup 14}/n, p/C{sup 14} v gazovoj i zhidkoj fazah. Mozhno predpolozhit', chto v processe stabilizacii gorjachie atomy ugleroda obrazujut metilenovye biradikaly, kotorye po svoej sposobnosti vstupat' v reakciju vo mnogom napominajut povedenie atomarnoj sery. Issledovanija provodilis' kak dlja parafinovyh (CH{sub 4}, C{sub 2}H{sub 6}), tak i dlja ciklicheskih (ciklogeksan, ciklogeksen, benzol) uglevodorod. Oblucheniju podvergalis' binarnye sistemy uglevodorod-datchik gorjachih atomov S{sup 35} i C{sup 14}. V kachestve poslednego ispol'zovalis' soedinenija CCI{sub 4}, HCl i ammiak. Obluchenie provodilos' na reaktore tipa IRT-1000 pri potoke teplovyh nejtronov 10{sup 11} - 10{sup 12} neJtron/cm{sup 2}sek. Pokazano, chto dlja razlichnyh soedinenij v zhidkoj faze do 60-90% sery-35 stabilizuetsja v forme polimera, vyhod kotorogo jekstremal'no zavisit ot sostava, prohodja cherez maksimum pri sootnoshenii komponentov, blizkom k jekvimolekuljarnomu. V gazovoj faze vyhod polimera sostavljaet 30 - 40% ot obshhej aktivnosti. Metodom radiohromatografii na bumage ustanovleno, chto mechenye polimernye produkty imejut slozhnyj sostav i predstavljajut soboj smes' dvuh kachestvenno otlichnyh tipov soedinenij, vyhod kotoryh po-raznomu menjaetsja v zavisimosti ot sootnoshenija komponentov. Uvelichenie vremeni obluchenija privodit k rostu vyhoda mechenogo polimera. V sluchae zhidkofaznoj sistemy C{sub 6}H{sub 12}-CCl{sub 4} molekuljarnyj ves S{sup 35}-soderzhashhego polimera, opredeljalsja metodom diffuzii iz kapilljara i okazalsja ravnym 5000 dlja polimera odnogo tipa i 500 - 1000 dlja drugogo. Obrazovanie vysokokipjashhego mechenogo produkta nabljudalos' takzhe pri obluchenii chistogo CCI{sub 4}. Analogichnye opyty provodilis' v sisteme jetilen -ammiak v gazovoj faze pri vysokom davlenii. Pokazano, chto v jetom sluchae pri obluchenii chistogo bezvodnogo ammiaka osnovnym mechenym produktom javljaetsja C{sup 14}H{sub 4}. Odnako uzhe malye dobavki jetilena privodjat k tomu, chto znachitel'naja dolja (do 80%) C{sup 14} stabiliziruetsja v forme polimera, vyhod kotorogo takzhe menjaetsja jekstremal'no s rostom doli jetilena v sisteme, dostigaja maksimuma pri 10 - 15% C{sub 2}H{sub 4}. Pokazano, chto vid krivoj vyhoda polimera C{sup 14} ne menjaetsja s uvelicheniem moshhnosti dozy i potoka. (author)}
place = {IAEA}
year = {1965}
month = {Apr}
}