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.

Characterisation of blends based on hydroxyethylcellulose and maleic acid-alt-methyl vinyl ether

Hydrophilic polymeric films based on blends of hydroxyethylcellulose and maleic acid-co-methyl vinyl ether were produced by casting from aqueous solutions. The physicochemical properties of the blends have been assessed using Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, dielectric spectroscopy, etc. The pristine films exhibit complete miscibility due to the formation of intermacromolecular hydrogen bonding. The thermal treatment of the blend films leads to cross-linking via intermacromolecular esterification and anhydride formation. The cross-linked materials are able to swell in water and their swelling degree can be easily controlled by temperature and thermal treatment time. The formation of the crosslinks is apparent in the dynamic properties of the blends as observed through the mechanical relaxation and dielectric relaxation spectra. The dielectric characteristics of the material are influenced by the effects of change in the local structure of the blend on the ionic conduction processes and the rate of dipolar relaxation. Separation of these processes is attempted using the dielectric modulus method. Significant deviations from a simple additive rule of mixing on the activation energy are observed consistent with hydrogen bonding and crosslinking of the matrix. This paper indicates a method for the creation of films with good mechanical and physical characteristics by exposing the blends to a relatively mild thermal treatment.

Investigation of cadmium alternatives in thin-film coatings - art. no. 62860C

The health risks associated with the inhalation or ingestion of cadmium are well documented([1,2]). During the past 18 years, EU legislation has steadily been introduced to restrict its use, leaving a requirement for the development of replacement materials. This paper looks at possible alternatives to various cadmium II-VI dielectric compounds used in the deposition of optical thin-films for various opto-electronic devices. Application areas of particular interest are for infrared multilayer interference filter fabrication and solar cell industries, where cadmium-based coatings currently find widespread use. The results of single and multilayer designs comprising CdTe, CdS, CdSe and PbTe deposited onto group IV and II-VI materials as interference filters for the mid-IR region are presented. Thin films of SnN, SnO2, SnS and SnSe are fabricated by plasma assisted CVD, reactive RF sputtering and thermal evaporation. Examination of these films using FTIR spectroscopy, SEM, EDX analysis and optical characterisation methods provide details of material dispersion, absorption, composition, refractive index, energy band gap and layer thicknesses. The optimisation of deposition parameters in order to synthesise coatings with similar optical and semiconductor properties as those containing cadmium has been investigated. Results of environmental, durability and stability trials are also presented.

Towards a THz osmometer

This work discusses the use of a THz-transient spectrometer for the measurement of tissue water content. The relation of both mammalian- and plant-cell water content to the osmotic potential is discussed. The process of equilibration of tissue water potential with the water potential of water vapor in an osmometer cuvette is described. Observation of the THz transmittance through the water vapor provides a measure of the water activity and water potential in the sample. The possibility of performing dielectric relaxation measurements of the liquid water in the tissue at THz frequencies directly and the use of proline as marker of water stress in tissue are discussed.

On the electrical properties of insulation oils

Insulating oils are a major component of high voltage plant, including transformers, switchgear and cables. Consequentially, in terms of plant failure, changes in the electrical characteristics of the oil during ageing are of crucial importance. To address this issue, commercial insulating oil was subjected to controlled ageing under laboratory conditions. The electrical properties of the aged oils were then characterized using dielectric spectroscopy. The data suggest that a degree of electrical conductivity occurs in the aged oils, which reduces the insulating properties of the oil as ageing proceeds. The role of atmosphere and additives on the electrical properties of the oils were also explored. Results are compared with model samples, which contain known amounts of materials that may occur as by-products of the ageing process.

Comparative study of Barium Fluoride thin films produced by ion-beam sputtering and thermal evaporation

Coatings and filters for spaceflight far-infrared components require a robust, non-absorptive low-index thin film material to contrast with the typically higher refractive index infrared materials. Barium fluoride is one such material for the 10 to 20µm wavelength infrared region, however its optical and mechanical properties vary depending on the process used to deposit it in thin film form. Thin films of dielectric produced by thermal evaporation are well documented as having a lower packing density and refractive index than bulk material. The porous and columnar micro structure of these films causes possible deterioration of their performance in varied environmental conditions, primarily because of the moisture absorption. Dielectric thin films produced by the more novel technique of ion-beam sputtering are denser with no columnar micro structure and have a packing density and refractive index similar to the bulk material. A comparative study of Barium Fluoride (BaF2) thin films made by conventional thermal evaporation and ion-beam sputtering is reported. Films of similar thicknesses are deposited on Cadmium Telluride and Germanium substrates. The optical and mechanical properties of these films are then examined. The refractive index n of the films is obtained from applying the modified Manifacier's evvelope method to the spectral measurements made on a Perkin Elmer 580 spectrophotometer. An estimate is also made of the value of the extinction coefficient k in the infrared wavelength transparent region of the thin film. In order to study the mechanical properties of the BaF2 films, and evaluate their usefulness in spaceflight infrared filters and coatings, the thin film samples are subjected to MIL-F-48616 environmental tests. Comparisons are made of their performance under these tests.

Synthesis of broadband anti-reflection coatings for spaceflight infrared optics

A synthesis method is outlined for the design of broadband anti-reflection coatings for use in spaceborne infrared optics. The Golden Section optimisation routine is used to make a search, using designated non-absorptive dielectric thin film combinations, for the coating design which fulfils the required spectral requirements using the least number of layers and different materials. Three examples are given of coatings designed by this method : (I) 1µm to 12µm anti-reflection coating on Zinc Sulphide using Zinc Sulphide and Yttrium Fluoride thin film materials. (ii) 2µm to 14µm anti-reflection coating on Germanium using Germanium and Ytterbium Fluoride thin film materials. (iii) 6µm to 17µm anti-reflection coating on Germanium using Lead Telluride, Zinc Selenide and Barium Fluoride. The measured spectral performance of the manufactured 6µm to 17µm coating on Germanium is given. This is the anti-reflection coating for the germanium optics in the NASA Cassini Orbiter CIRS instrument.

Synthesis of infrared filters for use in spaceflight systems

Progress is reported in the development of a new synthesis method for the design of filters and coatings for use in spaceborne infrared optics. This method uses the Golden Section optimization routine to make a search, using designated dielectric thin film combinations, for the coating design which fulfills the required spectral requirements. The final design is that which uses the least number of layers for the given thin film materials in the starting design. This synthesis method has successfully been used to design broadband anti-reflection coatings on infrared substrates. The 6 micrometers to 18 micrometers anti-reflection coating for the germanium optics of the HIRDLS instrument, to be flown on the NASA EOS-Chem satellite, is given as an example. By correctly defining the target function to describe any specific type of filter in the optimization part of the method, this synthesis method may be used to design general filters for use in spaceborne infrared optics.

An ultra-wide passband (5-30µm) filter for FTIR studies of Photosystem II

This paper reports on the design and manufacture of an ultra-wide (5-30µm) infrared edge filter for use in FTIR studies of the low frequency vibrational modes of metallo-proteins. We present details of the spectral design and manufacture of such a filter which meets the demanding bandwidth and transparency requirements of the application, and spectra that present the new data possible with such a filter. A design model of the filter and the materials used in its construction has been developed capable of accurately predicting spectral performance at both 300K and at the reduced operating temperature at 200K. This design model is based on the optical and semiconductor properties of a multilayer filter containing PbTe (IV-VI) layer material in combination with the dielectric dispersion of ZnSe (II-VI) deposited on a CdTe (II-VI) substrate together with the use of BaF2 (II-VII) as an antireflection layer. Comparisons between the computed spectral performance of the model and spectral measurements from manufactured coatings over a wavelength range of 4-30µm and temperature range 300-200K are presented. Finally we present the results of the FTIR measurements of Photosystem II showing the improvement in signal to noise ratio of the measurement due to using the filter, together with a light induced FTIR difference spectrum of Photosystem II.

Performance model for cooled IR filters

A low-temperature model is described for infrared multilayer filters containing PbTe (or other semiconductor) and ZnSe (or other II/VI). The model is based on dielectric dispersion with semiconductor carrier dispersion added. It predicts an improved performance on cooling such as would be useful to avoid erroneous signals from optics in spaceflight radiometers. Agreement with measurement is obtained over the initial temperature range 70-400K and wavelength range 2.5-20µm.

Optical thin films

Optical thin films are coatings of amorphous, crystalline or polymerized materials, in single or multiple layers, on surfaces of optical components such as lenses and mirrors. These thin film coatings are used in optics to reduce reflections from optical parts (antireflection coatings) or to provide highly reflective surfaces (dielectric mirrors), as well as to protect components against abrasion and ambient moisture.

Cooled filters 16-42µm for FIR astronomy

The design and manufacture of dielectric-film interference filters for cooled FIR stronmy is described. The bands are 16.5-21.5µm, 17.5-19.5µm, 19.5-21.5µm and 27µm cut on. The films are PbTe/CdSe and the substrates are CdTe (some 1/2 mm thick), without absorption in the region: KRS-6 films are used for antireflection.

A Monte Carlo study of solutions of oppositely charged polyelectrolytes

The formation of complexes appearing in solutions containing oppositely charged polyelectrolytes has been investigated by Monte Carlo simulations using two different models. The polyions are described as flexible chains of 20 connected charged hard spheres immersed in a homogenous dielectric background representing water. The small ions are either explicitly included or their effect described by using a screened Coulomb potential. The simulated solutions contained 10 positively charged polyions with 0, 2, or 5 negatively charged polyions and the respective counterions. Two different linear charge densities were considered, and structure factors, radial distribution functions, and polyion extensions were determined. A redistribution of positively charged polyions involving strong complexes formed between the oppositely charged polyions appeared as the number of negatively charged polyions was increased. The nature of the complexes was found to depend on the linear charge density of the chains. The simplified model involving the screened Coulomb potential gave qualitatively similar results as the model with explicit small ions. Finally, owing to the complex formation, the sampling in configurational space is nontrivial, and the efficiency of different trial moves was examined.