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In the present work, scanning tunneling microscopy (STM) was employed to study the surface modification of ultrahigh modulus carbon fibers at the atomic level by oxygen plasma. As detected by STM, the distinctive feature of the fresh, untreated surface was the general presence of atomic-scale arrangements in different degrees of order (from atomic-sized spots without a clearly ordered disposition to triangular patterns identical to those typical of perfect graphite). Following fiber exposure to the plasma, the STM images showed evidence of the abstraction of carbon atoms from random locations on the fiber surface, giving rise to the development of defects (i.e., structural disorder), which in turn were the places where oxygen could be introduced during and after the plasma etching. It was observed that the most effective treatments in terms of extent of surface structural modification (disordering) and uniform introduction of oxygen were those carried out for just a few ( approximately 3) minutes. Considerably shorter exposures failed to provide a homogeneous modification and many locations on the fiber surface remained unaltered, retaining their original atomic-scale order, whereas longer treatments did not bring about further structural changes to the surface and only led to fiber consumption. These results are consistent with previous X-ray photoelectron spectroscopy measurements on these fibers and provide an atomic-level understanding of the saturation effect observed in the surface oxygen concentration of this and other types of carbon fibers with plasma oxidation. Such understanding may also prove helpful for the accurate control and optimization of fiber-matrix interaction in composite materials.

Carbon composites were prepared with four pitches (a commercial impregnating coal-tar pitch, two thermally treated pitches and an air-blown pitch) and four granular carbons (anthracite, graphite, green petroleum coke and foundry coke). Granular carbon/pitch proportions were optimized for each composite and differed in the characteristics of the single components. Interactions of the pitch with the granular carbons during pyrolysis and their subsequent effects on the microstructure of the final composite were monitored by light microscopy. The results show that the light texture of the matrix and the porosity of the composite depend not only on the chemical composition of the pitch but also on the specific granular carbon used as reinforcing material. The same pitch may generate different light textures depending on the characteristics of the carbon. Composites from thermally treated pitches and graphite show highly ordered matrices orientated in the direction of graphite planes. Graphite particles seem to exert a huge influence on mesophase development during the pyrolysis of the treated pitches, affecting not only the orientation of the mesophase, but also reducing the rate of mesophase formation. On the other hand, when green petroleum coke is used with the thermally treated pitches, matrices show a small size light texture, due to the high reactivity of the pitch in the presence of this granular carbon. The porosity of the composites is controlled by both the pitch and the granular carbon.

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (<800 degrees C), NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range (>800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

Here we report, for the first time, the high resolution imaging of hydrophilic, polar functional group distributions on flat carbon surfaces by phase contrast in noncontact tapping mode AFM.

The objective of this work was to characterize the degree of heterogeneity brought about by oxygen plasma treatment of carbon fibers by studying its effects on the adsorption of n-alkanes. Untreated and unsized high-strength carbon fibers were subjected to oxygen plasma treatments with different degrees of severity. A sample of the same material oxidized following a standard industrial method was also studied for comparison. Adsorption of C5-C10n-alkanes at 303-353 K was measured by inverse gas chromatography (IGC). Elution peaks were symmetrical for the fresh and industrially oxidized samples; however, a large extent of asymmetry was observed for the plasma-treated fibers. Differences in surface heterogeneity were quantified in terms of several adsorption thermodynamic magnitudes. Differential heats of adsorption exhibited values similar to those corresponding to the probe-basal plane interaction. The dispersive component of the surface tension of the solids increased clearly upon plasma oxidation, the increase being systematic according to the severity of plasma treatment. It can be concluded that plasma oxidation generates high-surface-energy sites responsible for trapping of n-alkane molecules, this effect being more marked as the chain length increases. The possibility of this effect being associated to creation of micropores was ruled out on the basis of volumetric CO2 adsorption experiments and IGC measurements at finite dilution. Scanning tunneling microscopy observations allowed us to establish a possible connection between fiber surface nanostructure and IGC results. The sites accessible to n-alkane molecules in the industrially oxidized sample seem to be highly disordered, thus leading to a weaker interaction with the adsorbate.

Tars produced at semi-industrial scale in a coke oven of 6 x 10(3) kg capacity were used to investigate the effect of using polyethylene waste as an additive in the carbonization process with coal. The polyethylene wastes used were low-density polyethylene from the agriculture greenhouses and high-density polyethylene from domestic sources. The high-performance liquid chromatography analysis of the soluble fractions in toluene and carbon disulfide, using two polystyrene-divinylbenzene columns and a mixture of dichloromethane-methanol as a mobile phase, provides useful information on the composition of tars and their derived pitches in terms of the substitution and molecular topology of polynuclear aromatic compounds (PACs). Differences in composition of tars produced with polyethylene waste at 1% (w/w) have been found to be negligible, while a higher amount of the waste (3%, w/w) promoted the formation of peri-condensed PACs at the expense of the substituted cata-condensed PACs. This behaviour is due to more extensive secondary reactions of tar precursors via dealkylation and aromatic condensation taking place during the carbonization process as a consequence of a more viscous co-carbonizing system. Changes in tar composition caused by this amount of polyethylene waste addition were comparable to those promoted by an increase in the carbonization temperature at semi-industrial and industrial ovens and by the coal preheating before the carbonization process. The characteristic features in tar composition were also found for the derived pitches from tars obtained with the polyethylene waste addition.

The structure and composition of products from the reaction of anthracene oil with anhydrous AlCl3 have been examined. Size-exclusion chromatography has been carried out using a column with polystyrene-polydivinylbenzene as stationary phase, 1-methyl-2-pyrrolidinone at 80 degrees C as eluent and variable-wavelength UV-absorption detection. This system provides a chromatogram of the sample with several peaks. Molecular masses corresponding to these peaks were estimated using a calibration curve obtained with polycyclic aromatic hydrocarbon standards, ranging from 92 to 532 u. The most abundant compounds of the substrate were dimers and trimers of the main anthracene oil components. These results are corroborated on a qualitative level by synchronous UV-fluorescence spectra.

The aim of this study was to determine the volatile products distribution of co-processing of coal with two plastic wastes, low-density polyethylene from agriculture greenhouses and high-density polyethylene from domestic uses, in order to explain the observed decrease in coal fluidity caused by polyethylene waste addition. Polymeric materials, although they are not volatile themselves, may be analysed by gas chromatography through the use of pyrolysis experiments. In this way, a series of pyrolysis tests were performed at 400 and 500 degrees C in a Gray-King oven with each of the two plastic wastes, one high-volatile bituminous coal and blends made up of coal and plastic waste (9:1, w/w, ratio). The pyrolysis temperatures, 400 and 500 degrees C, were selected on the basis of the beginning and the end of the coal plastic stage. The organic products evolved from the oven were collected, dissolved in pyridine and analysed by capillary gas chromatography using a flame ionization detector. The analysis of the primary tars indicated that the amount of n-alkanes is always higher than that of n-alkenes and the formation of the alkenes is favoured by increasing the pyrolysis temperature. However, this effect may be influenced by the size of the hydrocarbon. Thus, the fraction C17-C31 showed a higher increase of n-alkenes/n-alkanes ratio than other fractions. On the other hand, the difference between the experimental and estimated values from tars produced from single components was positive for n-alkanes and n-alkenes, indicating that co-pyrolysis of the two materials enhanced the chemical reactivity during pyrolysis and produced a higher conversion than that from individual components.

Unidirectional carbon/carbon composites were prepared using polyacrylonitrile-based carbon fibres and a commercial coal-tar pitch. The preparation includes a three-sequential-step process: (i) prepreging, (ii) moulding/pressing, and (iii) carbonization to 1000 degrees C. The effect of the process parameters including pressure, mould characteristics, and temperature and duration of pressure application on the microstructure of composites was monitored by light microscopy. Results show that the application of a pressure of 1 MPa close to the temperature of pitch solidification produces lower porosity composites. This porosity is significantly reduced when the solidification of the pitch is tempered by the introduction of a soak time of 10 h at the temperature at which pressure is applied.

The aim of this paper is to study the applications of chromatography and related techniques in the transformation of coal-derived products into pitches for specific uses. Anthracene oil, tar and pitch were thermally treated in the presence of air (and sulfur in the case of anthracene oil) in order to cause the polymerization/condensation of their components. The evolution of the components of the parent materials during the treatments was monitored by gas chromatography-mass spectrometry, gas chromatography-atomic emission detection, probe mass spectrometry and size-exclusion chromatography. From the results obtained, possible mechanisms for the transformation of coal-derived products into new pitches were established.