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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS1984

Room-temperature luminescence from kaolin induced by organic amines

Several new, room-temperature luminescent phenomena, resulting from the interaction of kaolin and various amino compounds, have been observed. The emission of light from kaolin pastes (treated with quinoline, pyridine, hydrazine, monoethanolamine, n-butylamine, and piperidine) was shown to decay monotonically over a period of hours to days. More light was released by a given amino compound after it was dried and purified. Hydrazine, in addition to the monotonically decaying photon release, produces delayed pulses of light with peak emission wavelength of 365 nm which last between several hours and several days. These photon bursts are acutely sensitive to the initial dryness of the hydrazine, both in the number of bursts and the integrated photon output. The amount of light and the capacity of the kaolin to produce the delayed burst appeared to be strongly dependent on preliminary heating and on gamma-irradiation, analogous to the dehydration-induced light pulse previously reported from the Ames Research Center. A small, delayed burst of photons occurred when piperidine and n-butylamine were removed by evaporation into an H2SO4 reservoir.

Coyne, L. M.↗
NASA NTRS1983

Toughening mechanism in elastometer-modified epoxy resins: Part 1

Several plaques of Epon 828, cured with piperidine, modified with hycar(r) CTBN 1300X8, Hycar(R) CTBN 1300X13, and Hycar(R) CTBN 1300x15, and in some cases modified with biphenol A (BPA), yielded properly toughened epoxies with rubber particle diameters ranging from 0.1 to 10 microns. Fracture toughness experiments indicate that toughness was more a function of rubber content than the rubber particle size. Tensile volumetric behavior of the near resin exhibits two regions: an initial region where the increase in volume strain was due to the Poisson's effect, and a second region where a slower rate of increase in volume strain was due to shear deformation. Tensile volumetric deformation of an elastomer-modified epoxy exhibits the same type of behavior to that of the neat resin at low rates ( 3.2x0.01 sec(-1)). But at very high strain rates, which correspond more closely to the strain rates at the crack tip, there exists an increase in volume strain beyond the Poisson's effect. TEM, SEM and OM studies indicate that the rubber particles had voided. When a thin section from the deformed region is viewed under crossed-polarized light, shear bands are seen connecting voided rubber particles. From this information cavitation and enhanced shear band formation is proposed as the toughening mechanism.

Yee, A. F.↗
NASA NTRS1984

Toughening mechanism in elastomer-modified epoxy resins, part 2

The role of matrix ductility on the toughenability and toughening mechanism of elastomer-modified DGEBRA epoxies was investigated. Matrix ductility was varied by using epoxide resins of varying epoxide monomer molecular weights. These epoxide resins were cured using 4,4' diaminodiphenyl sulfone (DDS) and, in some cases, modified with 10% HYCAR(r)CTBN 1300X8. Fracture roughness values for the neat epoxies were found to be almost independent on the monomer molecular weight of the epoxide resin used. However, it was found that the fracture toughness of the elastomer-modified epoxies was very dependent upon the epoxide monomer molecular weight. Tensile dilatometry indicated that the toughening mechanism, when present, is similar to the mechanisms found for the piperidine cured epoxies in Part 1. SEM and OM corroborate this finding. Dynamic mechanical studies were conducted to shed light on the toughenability of the epoxies. The time-dependent small strain behavior of these epoxies were separated into their bulk and shear components. The bulk component is related to brittle fracture, whereas the shear component is related to yielding. It can be shown that the rates of shear and bulk strain energy buildup for a given stress are uniquely determined by the values of Poisson's ratio, nu. It was found that nu increases as the monomer molecular weight of the epoxide resin used increases. This increase in nu can be associated with the low temperature beta relaxation. The effect of increasing cross-link density is to shift the beta relaxation to higher temperatures and to decrease the magnitude of the beta relaxation. Thus, increasing cross-link density decreases nu and increases the tendency towards brittle fracture.

Yee, A. F.↗
NASA NTRS1994

Effect of leaving group on the oligomerization of 5'-AMP on montmorillonite

The oligomerization of imidazole derivative of 5'-AMP (ImpA) in the presence of montmorillonite clay yields oligomers containing up to 10 monomer units. In these reactions, the heterocyclic base, imidazole is the leaving group. In our present study, we synthesized a series of activated nucleotides of 5'AMP using other leaving groups such as pyrazole, 1,2,4-triazole, piperidine, morpholine, 4-aminopyridine, 4-methylaminopyridine, 4-dimethylaminopyridine, 2-aminobenzimidazole etc. to determine the effect of amine leaving group on the products of the oligomerization reaction. Earlier results from our laboratory showed that the presence AppA in the clay reaction of ImpA enhances the oligomerization reaction to yield higher oligomers. We also studied the effect of AppA in the clay mediated oligomerization reaction of the activated nucleotides. Oligomerization of 2-amino-benzimidazole derivative of 5'-AMP gave higher oligomers containing up to nine monomer units in the presence of AppA.

Prabahar, K. Joseph↗
NASA NTRS1994

Effect of phosphate activating group on oligonucleotide formation on montmorillonite: the regioselective formation of 3',5'-linked oligoadenylates

The effects of amine structure on the montmorillonite-catalyzed oligomerization of the 5'-phosphoramidates of adenosine are investigated. 4-Aminopyridine derivatives yielded oligoadenylates as long as dodecamers with a regioselectivity for 3',5'-phosphodiester bond formation averaging 88%. Linear and cyclic oligomers are obtained and no A5'ppA-containing products are detected. Oligomers as long as the hexanucleotide are obtained using 2-aminobenzimidazole as the activating group. A predominance of pA2'pA is detected in the dimer fraction along with cyclic 3',5'-trimer; no A5'ppA-containing oligomers were detected. Little or no oligomer formation was observed when morpholine, piperidine, pyrazole, 1,2,4-triazole, and 2-pyridone are used as phosphate-activating groups. The effects of the structure of the phosphate activating group on the oligomer structure and chain lengths are discussed.

Non-NASA Center↗
NASA NTRS1995

Large steric effect in the substitution reaction of amines with phosphoimidazolide-activated nucleosides

Aliphatic amines react with phosphoimidazolide-activated derivatives of guanosine and cytidine (ImpN) by replacing the imidazole group. The kinetics of reaction of guanosine 5'-phospho-2-methylimidazolide (2-MeImpG) with glycine ethyl ester, glycinamide, 2-methoxyethylamine, n-butylamine, morpholine, dimethylamine (Me2NH), ethylmethylamine (EtNHMe), diethylamine (Et2NH), pyrrolidine, and piperidine were determined in water at 37 degrees C. With primary amines, a plot of the logarithm of the rate constant for attack by the amine on the protonated substrate, log kSH(A), versus the pKa of the amine exhibits a good linear correlation with a Bronsted slope, beta nuc = 0.48. Most of the secondary amines tested react with slightly higher reactivity than primary amines of similar pKa. Interestingly, some secondary amines show substantially lower reactivity than might be expected: EtNHMe reacts about eight times, and Et2NH at least 100 times, more slowly than Me2NH although all three amines are of similar basicity. For comparison, the kinetics of reaction of guanosine 5'-phosphoimidazolide (ImpG) and cytidine 5'-phosphoimidazolide (ImpC) were determined with Me2NH, EtNHMe, and Et2NH, and similar results were obtained. These results establish that the increased steric hindrance observed with the successive addition of ethyl groups are not due to any special steric requirements imposed by the guanosine or the methyl on the 2-methylimidazole leaving group of 2-MeImpG. It is concluded that addition of ethyl and, perhaps, groups larger than ethyl dramatically increases the kinetic barrier for addition of aliphatic secondary amines to the P-N bond of ImpN. This study supports the observation that the primary amino groups on the natural polyamines are at least 2 orders of magnitude more reactive than the secondary amino groups in the reaction with ImpN.

Non-NASA Center↗