FT–IR spectroscopic study on the photo- and photooxidative degradation of nylons

The progress of photo- and photooxidative degradation of nylon films were studied by FT–IR spectroscopy. The gases evolved from the photolysis of various nylons and their model amides were also analyzed. The formation of double bonds, changes of crystallinity, and the effect of amino and carboxyl end groups has been studied and discussed. The band shapes of the IR spectra pertaining to the carbonyl groups formed by thermal oxidation or photooxidation were found to be very similar, suggesting that the two oxidation mechanisms might be similar. The broadness of these bands indicates that the carbonyl groups may belong to more than one species. The photodegradation of nylons containing purposely inserted carbonyl groups formed ? CH?CH₂ groups. Carbonyl groups formed during oxidation, and present either as keto groups or part of N-acylamide units make nylons susceptible to degradation reactions entailing mainly a Norrish type II mechanism.     

Compatibility studies of styrene and hydroxyl containing styrene copolymers with poly(ethylene oxide)

Copolymers of styrene with vinylphenyl trifluoromethyl carbinol, p-vinylphenyl trifluoromethyl carbinol, vinylphenyl hexafluorodimethyl carbinol, and p-vinylphenol are conditionally compatible with poly(ethylene oxide), depending on their composition and blending ratios, whereas copolymers of styrene and vinylphenyl methyl carbinol are much less compatible with poly(ethylene oxide), as determined by T_g criteria and differential scanning calorimetry. The crystallinity of poly(ethylene oxide) is changed in the copolymer/poly(ethylene oxide) blends, as indicated by depressions of the poly(ethylene oxide) melting point. Hydrogen-bond formation has been studied in two selected blends by infrared (IR) spectroscopy. Hydrogen bonding dissociation and reassociation as a function of temperature are reported. The conformation changes of poly(ethylene oxide) in the blends, the interaction between copolymer and poly(ethylene oxide) as well as in the reference blend, polystyrene/poly(ethylene oxide), are also investigated.     

Epoxy resins. III. Application of fourier transform IR to degradation studies of epoxy systems

Three cured epoxy resins were investigated under various degradation conditions by Fourier transform infrared (FTIR) spectroscopy for measurement. The epoxy resins were the diglyadyl ethers of bisphenol A (DGEBA), phenolphthalein (DGEPP), and 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF). The thermal stability order of functional groups that incurred DGEBA was total methyl group ～ total benzene ring > methylene > p-phenylene > ether linkage > isopropylidene. The oxidative thermal and photodegradation processes were found to be related to the classical autocatalytical oxidation of aliphatic hydrocarbon segments. The Wieland rearrangement, Norrish-type reaction, Claisen rearrangement, and other possible degradation mechanisms were suggested by the data.     

FT–IR spectroscopic study on the thermal and thermal oxidative degradation of nylons

The effects of heat and oxygen on nylon films were studied by FT–IR spectroscopy. Nylons 6, 66 and nylons containing carbonyl groups in either the diamine or the diacid moiety were prepared. Nylon films cast on aluminum were studied in an environmental chamber under controlled conditions. The progress of chemical and physical changes was monitored by FT–IR spectroscopy. Thermal energy caused largely an increase in crystallinity due to annealing and also an increase of nonhydrogen-bonded amide groups, which seemed to entail mainly amide groups from the amorphous region. The intensities of IR absorption bands related to the folded structure reduced as soon as heating began. The IR spectra of the carbonyl groups formed by thermal oxidation showed band shapes that indicated that the formed carbonyl groups were of many different origins. The presence of keto groups purposely inserted into the backbone chains increased the rate of oxidation. Pyrolysis of the nylons was also studied to supplement data obtained at lower temperatures.     

A Gorizont neutron reflectometer—small-angle spectrometer based on the IN-06 pulsed neutron source

The Gorizont time-of-flight neutron reflectometer—small-angle spectrometer has been designed, manufactured, and assembled to operate with the IN-0 6 pulsed neutron source. The instrument has a vertical neutron scattering plane enabling research on liquid surfaces and interfaces. Model calculations of neutron spectra, beam profiles, and spectrometer resolutions have been performed via the Monte Carlo method. The spectrometer operates at wavelengths from 1.5 to 9 Å and ensures measurements in the momentum-transfer range of 0.003—1.5 Å^-1.     

Thermodynamics of nucleation in an internal oxide getter in silicon

Nucleation of precipitates of silicon dioxide is studied theoretically within the framework of the classical theory of nucleation. Elastic stresses, accompanying nucleation, are taken into account under the assumption that the nucleus and matrix are incoherent and the silicon is elastically isotropic. The results of a numerical calculation of the form and dimensions of the critical nucleus, the free energy of its formation, and the rate of nucleation as a function of the annealing temperature in the range 773–1473 K for oxygen concentrations in the starting single crystal of (0.4–1.4)·10¹⁸ cm^–3 are presented. It is shown that homogeneous nucleation of precipitates is, in principle, possible. The magnitude of the specific free energy of the interphase boundary is estimated based on the data obtained.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 25–29, August, 1988.     

Concerning the ‘Non-Specific’ Far Infrared Absorption of Polar Liquids

The far infrared spectra of dimethyl sulfoxide and several aliphatic nitriles have been studied with a view towards elucidating the mechanism responsible for the intense absorption bands which have been observed in this region. Spectra of pure liquids, solid DMSO, DMSO-d₆, CD₃CN, and dilute solutions in non-polar solvents are presented. The results are discussed in terms of the possible mechanisms proposed for these absorptions.     

Thermal degradation study of phenolphthalein polycarbonate

Phenolphthalein polycarbonate underwent complicated thermal degradation which included random scission, rearrangement, hydrolysis, Friedel-Crafts acylation, and cross-linking. The carbonate group and lactone ring were both susceptible to thermal deterioration. Kinetic parameters were determined from the dynamic TGA thermograms. During early stages of degradation the measured reaction order was nearly 1, which suggested a random chain scission mechanism. The measured activation energy was 42.6 kcal/mol, compared with 41.2 kcal/mol calculated from isothermal aging. The Arrhenius preexponential constant was 3.09 × 10¹¹ min^?1. Below 80% weight residue the plot of fractional weight against 1/T revealed that complicated reactions with different activation energies occurred simultaneously and resulted in a final overlap of TGA curves for different heating rates indicative of cross-linking and a lower preexponential constant. The reaction order changed and kept increasing in the last stages of degradation. Pyrolysis of this polymer was performed at 350°C under vacuum, followed by GC-mass spectroscopic identification of products. The volatile products (17.5%) contained CO₂, CO, O₂, H₂O, phenol, fluorenone, diphenyl carbonate, xanthone, anthraquinone, 2-hydroxylanthraquinone, 2-benzoxyanthraquinone, phenolphthalein, and trace amounts of benzoxyphenol and hydroquinone; the other 82.5% of products was insoluble gel. Functional group changes were examined by Fourier transform infrared spectroscopy (FT-IR). Lactone, carbonate, and aromatic absorptions decreased during degradation. Increasing absorptions at 1739, 1728, 1280–1200, and 1138–1075 cm^?1 were believed to result from aromatic ester (1728 cm^?1) and phenyl aromatic ester (1739 cm^?1) cross-linkages ortho to the aromatic ether group (increases at 1155 cm^?1 and 1280–1200 cm^?1). Existence of 2-hydroxyanthraquinone and xanthone contained in the crosslinked polymer matrix were also detected. Mechanisms for random scission, rearrangement, Friedel-Crafts acylation, hydrolysis, and cross-linking were suggested.     

Characteristics of the DIN-2PI spectrometer with a neutron concentrator

The basic characteristics of the upgraded DIN-2PI spectrometer are reported. Based on experimental data and numerical calculation results, it is concluded that a supermirror neutron concentrator, with which the DIN-2PI spectrometer is equipped, raises the density of the cold neutron flux at the sample almost by an order of magnitude. The use of a grooved moderator in channel no. 2 and upgrading of the core of the IBR-2M reactor increases the neutron flux density on the sample by about 40% more.