Chemical, physical and electrical properties of aged dodecylbenzene 3: thermal ageing of mixed isomers in nitrogen and under sealed conditions

Commercial dodecylbenzene cable fluid was aged at temperatures of 105 and 135 degrees C in dry oxygen-free nitrogen. In addition, selected samples were aged at 135 degrees C under sealed conditions where air was excluded from the headspace above the oil. A variety of analytical techniques, such as ultra-violet visible and infra-red spectroscopy, acid number and water content measurements, were then used to characterize the aged oils. In addition, their electrical properties were assessed by dielectric spectroscopy. Compared with ageing in air, the ageing rate was reduced significantly and, as expected, no major oxidation peaks were detected in the infrared spectrometer. Significantly, very little absorbance at 680 nm ("red absorbers") was detected in samples aged with copper and, consequentially, no large increases in dielectric loss were recorded within the ageing times considered here. This study compliments previous investigations on cable fluid and 1-phenyldodecane aged in air and show that the same ageing indicators are valid in oils aged under conditions which more closely resemble those found in high voltage plant.

Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.

Chemical, physical and electrical properties of aged dodecylbenzene 2: thermal ageing of single isomers in air

The linear isomer of dodecylbenzene (DDB), 1-phenyldodecane, was aged at temperatures of 105 and 135 degrees C in air and the resultant products were analyzed using a range of analytical techniques. On ageing, the 1-phenyldodecane darkened, the acid number, dielectric loss and water content increased and significant oxidation peaks were detected in the infrared spectrum. When aged in the presence of copper, a characteristic peak at 680 nm was also detected by UV/visible spectroscopy but, compared with previous studies of a cable-grade DDB, the strength of this peak was much increased and no appreciable precipitate formation occurred. At the same time, very high values of dielectric loss were recorded. On ageing in the absence of copper, an unusually strong infrared carbonyl band was seen, which correlates well with the detection of dodecanophenone by gas chromatography / mass spectrometry and nuclear magnetic resonance spectroscopy. It was therefore concluded that the ageing process proceeds via the initial production of aromatic ketones, which may then be further oxidized to carboxylic acids. In the presence of copper, these oxidation products are present in lower quantities, most of these oxidation products being combined with the copper present in the oil to give copper carboxylates. The behavior is described in terms of a complex autoxidation mechanism, in which copper acts as both an oxidizing and a reducing agent, depending on its oxidation state and, in particular, promotes elimination via the oxidation of intermediate alkyl radical species to carbocations.

System identification algorithms for the analysis of dielectric responses from broadband spectroscopies

We discuss the modeling of dielectric responses for an electromagnetically excited network of capacitors and resistors using a systems identification framework. Standard models that assume integral order dynamics are augmented to incorporate fractional order dynamics. This enables us to relate more faithfully the modeled responses to those reported in the Dielectrics literature.

Multivariate analysis of the dielectric response of materials modeled using networks of resistors and capacitors

We discuss the modeling of dielectric responses of electromagnetically excited networks which are composed of a mixture of capacitors and resistors. Such networks can be employed as lumped-parameter circuits to model the response of composite materials containing conductive and insulating grains. The dynamics of the excited network systems are studied using a state space model derived from a randomized incidence matrix. Time and frequency domain responses from synthetic data sets generated from state space models are analyzed for the purpose of estimating the fraction of capacitors in the network. Good results were obtained by using either the time-domain response to a pulse excitation or impedance data at selected frequencies. A chemometric framework based on a Successive Projections Algorithm (SPA) enables the construction of multiple linear regression (MLR) models which can efficiently determine the ratio of conductive to insulating components in composite material samples. The proposed method avoids restrictions commonly associated with Archie’s law, the application of percolation theory or Kohlrausch-Williams-Watts models and is applicable to experimental results generated by either time domain transient spectrometers or continuous-wave instruments. Furthermore, it is quite generic and applicable to tomography, acoustics as well as other spectroscopies such as nuclear magnetic resonance, electron paramagnetic resonance and, therefore, should be of general interest across the dielectrics community.

Wavelet based detection of changes in the composition of RLC networks

The current work discusses the compositional analysis of spectra that may be related to amorphous materials that lack discernible Lorentzian, Debye or Drude responses. We propose to model such response using a 3-dimensional random RLC network using a descriptor formulation which is converted into an input-output transfer function representation. A wavelet identification study of these networks is performed to infer the composition of the networks. It was concluded that wavelet filter banks enable a parsimonious representation of the dynamics in excited randomly connected RLC networks. Furthermore, chemometric classification using the proposed technique enables the discrimination of dielectric samples with different composition. The methodology is promising for the classification of amorphous dielectrics.