925 resultados para Thermal neutron fluence


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The thermal decomposition of 2,3-di~ethy l - J-hydr operox y- 1 - butene , p r epared f rol") singl e t oxygen, has been studied i n three solvents over the tempe r a ture r ange from 1500e to l o00e and t!1e i 111 t ial ~oncentrfttl nn r Ange from O. 01 M to 0.2 M. Analys i s of the kine tic data ind ica te s i nduced homolysis as the n ost probRble mode of d e composition, g iving rise to a 3/2 f S order dependence upon hy d.roperoxide concent :r8.tl on . Experimental activation e nergies for the decomposition were f ound to be between 29.5 kcsl./raole and 30.0 k cal./mole .• \,iith log A factors between 11 . 3 and 12.3. Product studies were conducted in R variety of solvents a s well as in the pr esence of a variety of free r adical initiators . Investigation of the kinetic ch a in length indicated a chain length of about fifty. A degenerat i ve chain branching mechanism 1s proposed which predicts the multi t ude of products which Rre observed e xperimentally as well as giving activation energies and log A factors si~il a r to those found experimentally .

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Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.

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:ofiedian lethal temperatures ( LT50' s ) were determined for rainbow trout, Salmo gairdnerii, acclimated for a minimum of 21 days at 5 c onstant temperatures between 4 and 20 0 C. and 2 diel temperature fluctuations ( sinewave curves of amplitudes ± 4 and ± 7 0 C. about a mean temperature of 12 0 C. ) . Twenty-four-, 48-, and 96-hour LT50 estimates were c alculated f ollowing standard flow-through aquatic bioassay techniques and probi t transformation of mortality data. The phenomenon of delayed thermal mortality was also investigated. Shifts in upper incipient lethal temperature occurred as a result of previous thermal conditioning. It was shown that increases in constant acclimation temperature result in proportional l inear increases in thermal tolerances. The increase i n estimated 96-hour LT50's was approximately 0.13 0 c. X 1 0 C:1 between 8 and 20 0 C. The effect of acclimation to both cyclic temperature regimes was an increase in LT50 to values between the mean and maximum constant equivalent daily temperatures of the cycles. Twenty-four-, 48-, and 96-hour LT50 estimates of both cycles corresponded approximately to the LT50 values of the 16 0 C. c onstant temperature equivalent . This increase i n thermal tolerance was further demonstrated by the delayed thermal mortality experiments . Cycle amplitudes appeared to i nfluence thermal resistance through alterations in initi al mortality since mortality patterns characteristic of base temperature acclimations re-appeared after approximately 68 hours exposure to test temperatures for the 12 + 4 0 C. group, whereas mortality patterns stabilized and remained constant for a period greater than 192 hours with the larger therma l cycle ( 12 + 7 0 C. ). NO s ignificant corre lations between s pecimen weight and time-to-death was apparent. Data are discussed in relation to the establishment of thermal criteria for important commercial and sport fishes , such as the salmonids , as is the question whether previously reported values on lethal temperature s may have been under estimated.

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Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

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Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

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Rates of H2 formation have been determined for the thermal decomposition of isopropyl peroxide at l30o-l50oC in toluene and methanol and at l400C in isopropyl alcohol and water. Product studies have been carried out at l400C in these solvents. The decomposition of isopropyl peroxide was shown to be unimolecular with energies of activation in toluene, and methanol of 39.1, 23.08 Kcal/mole respectively. It has been shown that the rates of H2 formation in decomposition of isopropyl peroxide are solvent dependent and that the ~ vs "'2';' values (parameters for solvent polarity) givesastraight line. Mechanisms for hydrogen production are discussed which satisfactorily explain the stabilization of the six-centered transition state by the solvent. One possibility is that of conformation stabilization by solvent and the other, a transition state with sufficient ionic character to be stabilized by a polar solvent. Rates of thermal decomposition of 1,2-dioxane in tert-butylbenzene at l40o-l70oC have been determined. The activation energy was found to be 33.4 Kcal/mole. This lower activation energy, compared to that for the decomposition of isopropyl peroxide in toluene (39.1 Kcal/mole) has been explained in terms of ring strain. Decomposition of 1,2 dioxane in MeOH does not follow a first order reaction. Several mechanisms have been suggested for the products observed for decomposition of 1;2-dioxane in toluene and methanol.

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Type 1 Diabetes Mellitus (T1DM) is an autoimmune disease that destroys pancreatic beta cells, affecting glucose homeostasis. In T1DM, glucoregulation and carbohydrate oxidation may be altered in different ambient temperatures; however, current literature has yet to explore these mechanisms. This study examines the effects of 30 minutes of exercise at 65% VO2max in 5ºC, 20ºC and 35ºC in individuals with T1DM. No significant differences were observed for blood glucose across the 3 conditions (p = 0.442), but significance was found for core temperature, heat storage, and sweat rate (p < 0.01). Blood glucose was also shown to vary greatly between individuals among conditions. The mechanisms behind the differences in blood glucose may be due to the lack of significant glucagon production among conditions. These findings suggest that T1DM individuals may exercise submaximally for 30 minutes in different ambient temperatures without significant differences in glucoregulation.

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Lead chromium oxide is a photoconductive dielectric material tha t has great potential of being used as a room temperature photodetector. In this research, we made ceramic pellets of this compound as well as potassium doped compound Pb2-xKxCr05, where x=O, 0.05, 0.125. We also investigate the properties of the lanthanum doped sample whose chemical formula is Pb1.85Lao.15Cr05' The electronic, magnetic and thermal properties of these materials have been studied. Magnetization measurements of the Pb2Cr05 sample indicate a transition at about 310 K, while for the lanthanum doped sample the transition temperature is at about 295 K indicating a paramagnetic behavior. However, the potassium doped samples are showing the transition from paramagnetic state to diamagnetic state at different temperatures for different amounts of potassium atoms present in the sample. We have studied resistivity as a function of temperature in different gas environments from 300 K to 900 K. The resistivity measurement of the parent sample indicates a conducting to insulating transition at about 300 K and upon increasing the temperature further, above 450 K the sample becomes an ionic conductor. As temperature increases a decrease in resistance is observed in the lanthanum/potassium doped samples. Using Differential Scanning Calorimetry experiment an endothermic peak is observed for the Pb2Cr05 and lanthanum/potassium doped samples at about 285 K.

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Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

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Rattlesnakes use their facial pit organs to sense external thermal fluctuations. A temperature decrease in the heat-sensing membrane of the pit organ has the potential to enhance heat flux between their endothermic prey and the thermal sensors, affect the optimal functioning of thermal sensors in the pit membrane and reduce the formation of thermal ‘‘afterimages’’, improving thermal detection. We examined the potential for respiratory cooling to improve strike behaviour, capture, and consumption of endothermic prey in the South American rattlesnake, as behavioural indicators of thermal detection. Snakes with a higher degree of rostral cooling were more accurate during the strike, attacking warmer regions of their prey, and relocated and consumed their prey faster. These findings reveal that by cooling their pit organs, rattlesnakes increase their ability to detect endothermic prey; disabling the pit organs caused these differences to disappear. Rattlesnakes also modify the degree of rostral cooling by altering their breathing pattern in response to biologically relevant stimuli, such as a mouse odour. Our findings reveal that low humidity increases their ability to detect endothermic prey, suggesting that habitat and ambush sites election in the wild may be influenced by external humidity levels as well as temperature.

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Infrared thermography is a non-invasive technique that measures mid to long-wave infrared radiation emanating from all objects and converts this to temperature. As an imaging technique, the value of modern infrared thermography is its ability to produce a digitized image or high speed video rendering a thermal map of the scene in false colour. Since temperature is an important environmental parameter influencing animal physiology and metabolic heat production an energetically expensive process, measuring temperature and energy exchange in animals is critical to understanding physiology, especially under field conditions. As a non-contact approach, infrared thermography provides a non-invasive complement to physiological data gathering. One caveat, however, is that only surface temperatures are measured, which guides much research to those thermal events occurring at the skin and insulating regions of the body. As an imaging technique, infrared thermal imaging is also subject to certain uncertainties that require physical modeling, which is typically done via built-in software approaches. Infrared thermal imaging has enabled different insights into the comparative physiology of phenomena ranging from thermogenesis, peripheral blood flow adjustments, evaporative cooling, and to respiratory physiology. In this review, I provide background and guidelines for the use of thermal imaging, primarily aimed at field physiologists and biologists interested in thermal biology. I also discuss some of the better known approaches and discoveries revealed from using thermal imaging with the objective of encouraging more quantitative assessment.

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Cette thèse est dédiée à l’étude des matériaux InMnP et GaMnP fabriqués par implantation ionique et recuit thermique. Plus précisément nous avons investigué la possibilité de former par implantation ionique des matériaux homogènes (alliages) de InMnP et GaMnP contenant de 1 à 5 % atomiques de Mn qui seraient en état ferromagnétique, pour des possibles applications dans la spintronique. Dans un premier chapitre introductif nous donnons les motivations de cette recherche et faisons une revue de la littérature sur ce sujet. Le deuxième chapitre décrit les principes de l’implantation ionique, qui est la technique utilisée pour la fabrication des échantillons. Les effets de l’énergie, fluence et direction du faisceau ionique sur le profil d’implantation et la formation des dommages seront mis en évidence. Aussi dans ce chapitre nous allons trouver des informations sur les substrats utilisés pour l’implantation. Les techniques expérimentales utilisées pour la caractérisation structurale, chimique et magnétique des échantillons, ainsi que leurs limitations sont présentées dans le troisième chapitre. Quelques principes théoriques du magnétisme nécessaires pour la compréhension des mesures magnétiques se retrouvent dans le chapitre 4. Le cinquième chapitre est dédié à l’étude de la morphologie et des propriétés magnétiques des substrats utilisés pour implantation et le sixième chapitre, à l’étude des échantillons implantés au Mn sans avoir subi un recuit thermique. Notamment nous allons voir dans ce chapitre que l’implantation de Mn à plus que 1016 ions/cm2 amorphise la partie implantée du matériau et le Mn implanté se dispose en profondeur sur un profil gaussien. De point de vue magnétique les atomes implantés se trouvent dans un état paramagnétique entre 5 et 300 K ayant le spin 5/2. Dans le chapitre 7 nous présentons les propriétés des échantillons recuits à basses températures. Nous allons voir que dans ces échantillons la couche implantée est polycristalline et les atomes de Mn sont toujours dans un état paramagnétique. Dans les chapitres 8 et 9, qui sont les plus volumineux, nous présentons les résultats des mesures sur les échantillons recuits à hautes températures : il s’agit d’InP et du GaP implantés au Mn, dans le chapitre 8 et d’InP co-implanté au Mn et au P, dans le chapitre 9. D’abord, dans le chapitre 8 nous allons voir que le recuit à hautes températures mène à une recristallisation épitaxiale du InMnP et du GaMnP; aussi la majorité des atomes de Mn se déplacent vers la surface à cause d’un effet de ségrégation. Dans les régions de la surface, concentrés en Mn, les mesures XRD et TEM identifient la formation de MnP et d’In cristallin. Les mesures magnétiques identifient aussi la présence de MnP ferromagnétique. De plus dans ces mesures on trouve qu’environ 60 % du Mn implanté est en état paramagnétique avec la valeur du spin réduite par rapport à celle trouvée dans les échantillons non-recuits. Dans les échantillons InP co-implantés au Mn et au P la recristallisation est seulement partielle mais l’effet de ségrégation du Mn à la surface est beaucoup réduit. Dans ce cas plus que 50 % du Mn forme des particules MnP et le restant est en état paramagnétique au spin 5/2, dilué dans la matrice de l’InP. Finalement dans le dernier chapitre, 10, nous présentons les conclusions principales auxquels nous sommes arrivés et discutons les résultats et leurs implications.

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Les collisions proton-proton produites par le LHC imposent un environnement radiatif hostile au détecteur ATLAS. Afin de quantifier les effets de cet environnement sur la performance du détecteur et la sécurité du personnel, plusieurs simulations Monte Carlo ont été réalisées. Toutefois, la mesure directe est indispensable pour suivre les taux de radiation dans ATLAS et aussi pour vérifier les prédictions des simulations. À cette fin, seize détecteurs ATLAS-MPX ont été installés à différents endroits dans les zones expérimentale et technique d'ATLAS. Ils sont composés d'un détecteur au silicium à pixels appelé MPX dont la surface active est partiellement recouverte de convertisseurs de neutrons thermiques, lents et rapides. Les détecteurs ATLAS-MPX mesurent en temps réel les champs de radiation en enregistrant les traces des particules détectées sous forme d'images matricielles. L'analyse des images acquises permet d'identifier les types des particules détectées à partir des formes de leurs traces. Dans ce but, un logiciel de reconnaissance de formes appelé MAFalda a été conçu. Étant donné que les traces des particules fortement ionisantes sont influencées par le partage de charge entre pixels adjacents, un modèle semi-empirique décrivant cet effet a été développé. Grâce à ce modèle, l'énergie des particules fortement ionisantes peut être estimée à partir de la taille de leurs traces. Les convertisseurs de neutrons qui couvrent chaque détecteur ATLAS-MPX forment six régions différentes. L'efficacité de chaque région à détecter les neutrons thermiques, lents et rapides a été déterminée par des mesures d'étalonnage avec des sources connues. L'étude de la réponse des détecteurs ATLAS-MPX à la radiation produite par les collisions frontales de protons à 7TeV dans le centre de masse a montré que le nombre de traces enregistrées est proportionnel à la luminosité du LHC. Ce résultat permet d'utiliser les détecteurs ATLAS-MPX comme moniteurs de luminosité. La méthode proposée pour mesurer et étalonner la luminosité absolue avec ces détecteurs est celle de van der Meer qui est basée sur les paramètres des faisceaux du LHC. Vu la corrélation entre la réponse des détecteurs ATLAS-MPX et la luminosité, les taux de radiation mesurés sont exprimés en termes de fluences de différents types de particules par unité de luminosité intégrée. Un écart significatif a été obtenu en comparant ces fluences avec celles prédites par GCALOR qui est l'une des simulations Monte Carlo du détecteur ATLAS. Par ailleurs, les mesures effectuées après l'arrêt des collisions proton-proton ont montré que les détecteurs ATLAS-MPX permettent d'observer la désintégration des isotopes radioactifs générés au cours des collisions. L'activation résiduelle des matériaux d'ATLAS peut être mesurée avec ces détecteurs grâce à un étalonnage en équivalent de dose ambiant.

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Malgré une vaste littérature concernant les propriétés structurelles, électroniques et ther- modynamiques du silicium amorphe (a-Si), la structure microscopique de ce semi-cond- ucteur covalent échappe jusqu’à ce jour à une description exacte. Plusieurs questions demeurent en suspens, concernant par exemple la façon dont le désordre est distribué à travers la matrice amorphe : uniformément ou au sein de petites régions hautement déformées ? D’autre part, comment ce matériau relaxe-t-il : par des changements homo- gènes augmentant l’ordre à moyenne portée, par l’annihilation de défauts ponctuels ou par une combinaison de ces phénomènes ? Le premier article présenté dans ce mémoire propose une caractérisation des défauts de coordination, en terme de leur arrangement spatial et de leurs énergies de formation. De plus, les corrélations spatiales entre les défauts structurels sont examinées en se ba- sant sur un paramètre qui quantifie la probabilité que deux sites défectueux partagent un lien. Les géométries typiques associées aux atomes sous et sur-coordonnés sont extraites du modèle et décrites en utilisant les distributions partielles d’angles tétraédriques. L’in- fluence de la relaxation induite par le recuit sur les défauts structurels est également analysée. Le second article porte un regard sur la relation entre l’ordre à moyenne portée et la relaxation thermique. De récentes mesures expérimentales montrent que le silicium amorphe préparé par bombardement ionique, lorsque soumis à un recuit, subit des chan- gements structuraux qui laissent une signature dans la fonction de distribution radiale, et cela jusqu’à des distances correspondant à la troisième couche de voisins.[1, 2] Il n’est pas clair si ces changements sont une répercussion d’une augmentation de l’ordre à courte portée, ou s’ils sont réellement la manifestation d’un ordonnement parmi les angles dièdres, et cette section s’appuie sur des simulations numériques d’implantation ionique et de recuit, afin de répondre à cette question. D’autre part, les corrélations entre les angles tétraédriques et dièdres sont analysées à partir du modèle de a-Si.

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The thermal properties of short Nylon-6 fiber-reinforced Styrene butadiene rubber (SBR) composites were studied by Thermogravimetric Analysis (TGA). The effect of epoxy-based bonding agent on thermal degradation of the gum and the composites was also studied. The thermal stability of the SBR was enhanced in the presence of Nylon-6 fibers and the stability of the composites increased in the presence of bonding agent. The epoxy resin did not significantly change the thermal stability of SBR gum vulcanizate. Results of kinetic studies showed that the degradation of SBR and the short nylon fiber-reinforced composites with and without bonding agents followed first-order kinetics.