We have used a continuous-wave carbon dioxide laser in a single-mode realization of cavity ring-down spectroscopy to measure absorption coefficients of water vapor at 944 cm(-1) for several temperatures in the range 270-315 K. The conventional description of water vapor infrared absorption is applied, in which the absorption is modeled in two parts consisting of local line absorption and the remaining residual absorption, which has become known as the water vapor continuum. This water vapor continuum consists of distinct water-water, water-nitrogen, and water-oxygen continua. The water-water continuum absorption coefficient is found to have a magnitude of C(s)(296 K) = (1.82+/-0.02) x 10(-22) cm(2) molecule(-1) atm(-1), and the water-nitrogen coefficient has a magnitude of C(n)(296 K) = (7.3 +/- 0.4) x 10(-25) cm(2) molecule(-1) atm(-1). The temperature dependences of both the water-water and the water-nitrogen continua are shown to be well represented by a model describing the expected behavior of weakly bound binary complexes. Using this model, our data yield dissociation energies of D(e) = (-15.9 +/- 0.3) kJ/mole for the water dimer and D(e) = (-3.2 +/- 1.7) kJ/mole for the water-nitrogen complex. These values are in excellent agreement with recent theoretical predictions of D(e) = -15.7 kJ/mole (water dimer) and D(e) = -2.9 kJ/mole (water-nitrogen complex), as well as the experimentally determined value of D(e) = (-15.3 +/- 2.1) kJ/mole for the water dimer obtained by investigators employing a thermal conductivity technique. Although there is reasonably good agreement with the magnitude of the continuum absorption coefficients, the agreement on temperature dependence is less satisfactory. While our results are suggestive of the role played by water dimers and water complexes in producing the infrared continuum, the uncertain spectroscopy of the water dimer in this spectral region prevents us from making a firm conclusion. In the meantime, empirical models of water vapor continuum absorption, essential for atmospheric radiative transfer calculations, should be refined to give better agreement with our low-uncertainty continuum absorption data.
The level of thermo-oxidative degradation in a series of unstabilized and unfilled nitrile rubbers (NBR) varying in acrylonitrile (ACN) content (18–43.5 wt%) was investigated on heat-aged samples (40–120 °C) by Attenuated Total Reflectance–Fourier Transform Infrared (ATR-FTIR) spectroscopy. A similar degradation profile evolution was observed regardless of ACN content with the generation of hydroxyl-, carbonyl-, and ester-based products with a concomitant loss of the 1,4-trans, 1,4-cis, and 1,2-vinyl butadienes. The magnitude of IR active group absorption loss is greatest in the lowest ACN NBR concentration and steadily lessens toward higher ACN levels (1,4-cis > 1,2-vinyl > 1,4-trans >> butadiene methylenes). The 18% ACN NBR possesses two distinct kinetically different degradation regimes (80–120 and 40–80 °C). Activation energies by carbonyl growth and 1,4-trans loss increase from 71 to 87 kJ mol−1 and from 71 to 79 kJ mol−1 respectively, for decreasing ACN (43.5–18%) content. The rate of consumption of the 1,4-trans butadiene group is mainly affected by thermo-oxidative carbonyl-based and addition-cross-linking reactions, the latter being lower in activation energy for low to mid ACN NBRs. The high oxidation rate behavior of the lowest acrylonitrile rubber is attributed to its higher oxygen permeability rates. Cross-linking due to addition-type reactions is favored for higher 1,4 unsaturation levels.
We report measurements of the water vapor continuum using infrared cavity ringdown spectroscopy at frequencies of 931.002, 944.195, and 969.104 cm Ϫ1. Our values of the water vapor continuum coefficients for self-broadening at Tϭ296 K are C s 0 (931 cm Ϫ1)ϭ2.23Ϯ0.17, C s 0 (944 cm Ϫ1) ϭ2.02Ϯ0.13, and C s 0 (969 cm Ϫ1)ϭ1.79Ϯ0.21ϫ10 Ϫ22 molecules Ϫ1 cm 2 atm Ϫ1. Our measurements are found to be in good agreement with the far wing line shape theory of Ma and Tipping, but we find that empirical models of the water vapor continuum, widely used in radiative transfer calculations, significantly overestimate the observed self-broadened continuum.
The service life of nitrile O-rings exposed to hydraulic fluid was determined by accelerated aging at nine temperatures and four immersion times. Tensile mechanical properties (elongation and low strain modulus), volume swell, compression set, and chemical crosslink density by solvent swell were measured. Calculated activation energies based on Arrhenius rate behavior ranged from 52 to 65 kJmol−1, approximately 20–30 kJmol−1 lower than nitrile rubber heat aged in air environments. Using a 50% loss of elongation as a failure criterion, an estimate of 15 yr of service life at 23 °C was calculated. This corresponds to a compression set of 50% and an increase of approximately 30% of the chemical crosslink density. Replacement of the plasticizer with the mineral oil and its additives increased total inorganic levels in degraded O-rings as measured by thermogravimetric analysis. Besides additional sulfur and sodium, energy dispersive spectroscopy identified the presence of phosphorous, chlorine, and potassium. Hydraulic oil additives are likely responsible in facilitating the O-ring degradation through lower energy pathways that accelerate nitrile rubber hardening.
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