Primary carbonization of an anisotropic ‘mesophase’ pitch compared to conventional isotropic pitch

The evolution during carbonization treatments of a 100% anisotropic pitch (pitch C) was compared to that of Ashland 240 (100% γ resins). The anisotropic pitch C results from a gas-sparge preparation leading to a composition of 93% β resins (QS-TI) and 7% γ resins (QS). It is made of a major component (QS-TI), in which droplets (100-300 nm in size) partially toluene soluble are distributed. The physicochemical, textural and microtextural evolutions of the two pitches were studied. During pitch C primary carbonization, anisotropic droplets grow by coalescence, then decompose into Brooks and Taylor mesophase spheres suspended in isotropic drops. These drops develop at the expense of the anisotropic matrix by a continuous regeneration of the small anisotropic droplets which feed the isotropic drops by diffusion process. Then inside these drops, mesophase spheres grow then coalesce and the behaviour of a conventional pitch is restored. These various molecular associations are due to absence of chemical events below 450 °C, leading to the global mass spectrum being constant. At 500 °C the material is homogeneously anisotropic though plastic, the metastable system is destroyed and the evolution of conventional pitches is recovered, i.e. above 550 °C macropores develop up to solidification at 600 °C (semi-coke stage).     

Analysis and modeling of mesophase sphere generation, growth and coalescence upon heating of a coal tar pitch

The present study has been undertaken aiming: (1) to provide an experimental procedure for measurement of characteristics of mesophase sphere formation from a coal tar pitch upon heating at 673-723 K in terms of the time-dependent changes in the population density and the radius distribution of the spheres and (2) to prove that the nucleation, growth and coalescence of the spheres are essential for quantitative explanation of the time-dependent changes. In regard to (1), this paper describes the conditions that are required in microscopic analysis of cross-sections of the bulk of heat-treated pitch for the conversion of the population density and the radius distribution of the cross-sectional circles into those of spheres on volume basis. Regarding (2), a model analysis demonstrates that the change in the radius distribution with time, as well as that in the population density of spheres, can quantitatively be predicted. The analysis also reveals that the spheres grow without undergoing coalescence in the early period, and the sphere coalescence commences after termination of sphere generation while the growth continues.     

Analysis of the carbonization and formation of coal tar pitch mesophase under dynamic conditions

Thermokinetic analysis of three pitch samples was carried out: coal tar pitch obtained from light coke oven tar (P), mesophase pitch after 10.5 h (MP1), and mesophase pitch after 12 h (MP2) thermopreparation at 410 °C. The process was realized in a continuous system with a 10 kg mass being charged to the reactor. It was demonstrated using Kissinger’s law that the temperature criterion, the first-order thermokinetics and the calculated Arrhenius law parameters fulfill the isokinetic effect when the classical routes of thermokinetic analysis of the samples prepared under dynamic conditions (at three heating rates) are used, which makes the qualitative interpretation of differences between these samples difficult. An alternative solution was proposed using the relative rate of thermal decomposition. The temperature ranges of the chemical reactions leading to the formation of mesophase structures, as well as the temperature ranges of the coking processes of the Fixed Carbon phase, were determined.     

Liquid crystal surface anchoring of mesophase pitch

Mesophase pitch, in common with other liquid crystalline substances, exhibits preferred angles of molecular orientation at its boundaries with other phases. These orientations, or surface anchoring states, are important because they influence the ultimate graphene layer arrangement in a variety of carbon materials where the pitch precursor encounters a composite filler, a free surface, a bubble cavity, or the surfaces of processing equipment such as a fiber spinneret. This paper presents experimentally determined anchoring states for two mesophase pitches at free surfaces, and on twenty solid substrates. Edge-on anchoring is found to be the most common state, occurring on the free surface, on some metals, on PTFE, and on all oxides with the exception of the lamellar material mica. The optical texture associated with the edge-on films is observed to be stable during carbonization up to 1200 °C. Face-on anchoring is observed on carbon graphene planes, mica and the metals Pt, Ni, and Ag. Trends in the data are discussed in terms of the strength of pitch/substrate intermolecular forces relative to π-π bonding between large discotic mesogens within the pitch. The implications for the structure and properties of carbon materials are discussed.     

Effect of oxidation pre-treatment at 220 to 270 °C on the carbonization and activation behavior of phenolic resin fiber

The effect of oxidation pre-treatment of a phenolic resin fiber was examined from two aspects: one is to examine if the pre-treatment can be a means to increase the yield of carbon fiber and activated carbon fiber (ACF), and the other is to study the effect of the pre-treatment on the carbonization and activation behavior. A phenolic resin fiber was oxidized in air at 220 to 270 °C and it was subsequently carbonized at 900 °C and activated by steam at 900 °C. The oxidation was found to affect significantly the subsequent carbonization process in the way that the yield of the carbonized fiber increased with the severity of the oxidation. On the other hand, the oxidation was found not to affect the chemical and physical properties of the carbonized fiber. The ACF produced from the oxidized fiber had almost same pore structure as the ACF produced from the non-treated fiber when compared at a same activation level. The maximum yield of ACF produced from the oxidized fiber was 1.13 times larger than the yield of ACF produced from the non-treated fiber. Thus we could increase the production yield of ACF significantly without losing its high adsorption performance.     

Characterization of the surface properties of nitrogen-enriched carbons by inverse gas chromatography methods

The characterization of the surface properties of carbonaceous materials by inverse gas chromatography (IGC) techniques is described. The cokes investigated were produced by the co-pyrolysis of a coal-tar pitch (CTP) with different amounts of polyacrylonitrile (PAN) as a possible method to synthesize carbonaceous materials enriched in nitrogen. IGC at infinite dilution and LSER (linear solvation energy relationship) techniques were used to determine the physical and chemical surface properties of the cokes. In general, the surface free energy of adsorption is due to both dispersive and specific interactions. The dispersive component of the surface free energy was determined using n-alkane probes. For the specific component, which is primarily due to acid-base interactions, different polar probes were used. The LSER method was applied to improve our understanding of the adsorption process in terms of molecular interactions. We show that, to characterize dispersive interactions using n-alkanes, the LSER and IGC methods are equivalent. On the other hand, with both methods we find that all the samples present acidic and basic characteristics. However, the sensitivity of the LSER method does not allow us to discriminate between the three samples in terms of specific interactions.     

Activation of coal tar pitch carbon fibres: Physical activation vs. chemical activation

Activated carbon fibres (ACF) are obtained mainly by physical activation with steam or carbon dioxide. Additionally, there are many papers dealing with chemical activation of carbon fibres, or a polymeric raw material, with several chemical agents like for example, phosphoric acid, zinc chloride, aluminium chloride,… Nevertheless, although it is well known that hydroxides are good activating agents, there are few papers about the activation of carbon fibres with KOH or NaOH. In the present work, ACF with high surface area are obtained by chemical activation with KOH and NaOH. Both chemical agents present different behaviour; thus, NaOH developed the highest value of porosity and KOH developed samples with narrower micropore size distribution. In order to compare the results with those obtained by physical activation, some ACF have been prepared using CO₂ activation. The main conclusion of this work is that by using chemical activation it is possible to obtain similar, or even higher, porosity (∼1 ml/g, ∼3000 m²/g) than by physical activation. However, chemical activation presents two important advantages: (1) a much higher yield (27-47% for chemical activation and 6% physical activation for ∼2500 m²/g activated carbon fibres) and (2) the surface of the fibres prepared by chemical activation is less damaged than by physical activation.     

Effect of carbonization on mechanical and tribological behavior of a copper-phenolic-based friction material

The effects of carbonization on the mechanical and tribological behavior of a copper/phenolic resin-based semi-metallic friction material were investigated. The results show that a lower carbonization rate leads to a material having higher compressive strength and hardness, as well as fewer cracks. A lower carbonization temperature results in a material with a weak XPS signal of the C-OH bond, while a higher carbonization temperature results in low C-H intensity and increased C-C intensity at the expense of C-H and CO/C-O groups. The material heat-treated to 400 °C has the highest compressive strength and hardness values. Heat-treating to higher temperature causes both values to decline. Both friction coefficient and wear are increased with increasing carbonization temperature. The material carbonized to 600 °C exhibits an optimum tribological performance. The worn surface of samples without heat treatment or heat-treated to lower temperatures is covered with a smooth but loosely-bonded layer of wear debris. Only a small amount of counter-face material is transferred to the sample surface. The worn surface of samples treated at higher temperatures is covered with rough sliding tracks. A significant amount of counter-face material is transferred onto the sample surface during the sliding. Carbonized samples demonstrate far better high-temperature heat/oxidation resistance than do non-carbonized samples.     

Effects of fullerene addition on the carbonization of synthetic naphthalene isotropic pitch

The toluene soluble fraction of fullerene soot, consisting of C₆₀ and C₇₀ and other fullerenes, was co-carbonized with synthesized isotropic pitch derived from naphthalene. Mixtures of fullerene and pitch gave carbons in higher yield than expected from their single carbonizations at fullerene contents <30 wt%. The fullerenes suppressed the expansion of the pitch during carbonizations, and changed the optical textures of resultant carbons. At levels of addition of fullerenes <30 wt%, no fullerenes could be detected in resultant carbons by spectroscopy, but were detected as spheres of ca. 10–20 nm diameter in the carbons by TEM. It is considered that fullerenes remove hydrogen from the naphthenic structures of the pitch and so alter carbonization characteristics. Hydrogenation breaks the spheroidal fullerene framework.     

Stabilization and carbonization behavior of pitch-model compounds treated with iodine or bromine

Effects of iodine or bromine treatments on the stabilization and carbonization of pitches were investigated by using five kinds of pitch-model compounds with different molecular structures. Iodine treatment significantly modified the thermal properties of compounds with condensed aromatic-rings, which resulted in a high carbon yield. In iodine treatment remarkable reaction was more easily achieved for compounds in the liquid state than in the solid one. In contrast, bromine treatment had a different polymerization reaction from that for iodine, which was effective in increasing carbon yield on even the compounds without condensed rings. This result supports the hypothesis that bromine treatment is independent of the chemical structure of parent pitches.     

Application of a high magnetic field in the carbonization process to increase the strength of carbon fibers

Carbon fibers produced from PAN (polyacrylonitrile) as a precursor are generally subjected to the three heat treatment processes of stabilization and carbonization followed by graphitization. Stabilized fibers were carbonized in a high magnetic field of 5 T imposed parallel to the fiber axis at a temperature of 1445 K and graphitized without a magnetic field at 2273 K. The tensile strength of these treated fibers is increased by 14% in comparison with those of no magnetic treatment. The reason why the imposition of the magnetic field could improve the strength of the fibers has been studied through microscopic observation of the fiber surface as well as a statistical analysis by use of Weibull distributions.     

Carbon-ceramic composites from coal tar pitch and clays: application as electrocatalyst support

Carbon-ceramic composites have been prepared and characterised by different techniques (electron microscopy, X-ray microanalysis, X-ray diffraction and cyclic voltammetry). The effect on the conductivity of the thermal treatment temperature of the composites and the structure of the starting ceramic has been analysed. The results demonstrate that the layered structure of the clay determines their conductivity. The composites prepared are conductors and the conductivity goes through a maximum with increasing thermal treatment. Platinum has been successfully deposited on the carbon-ceramic composite by chemical and electrochemical methods. A better distribution of platinum and smaller particle sizes are obtained by the electrochemical method. The direct electrooxidation of methanol in acid medium has been studied on platinum-modified carbon-ceramic electrodes.     

The influence of primary QI on the oxidation behaviour of pitch-based C/C composites

Three unidirectional C/C composites were prepared from PAN-based carbon fibres and three coal-tar pitches obtained from the same parent coal-tar pitch but differing in their primary QI content. The effect of the amount of primary QI present in pitches on the air reactivity of pitch-cokes and C/C composites was studied by thermogravimetric analysis. The oxidation of pitch-cokes was performed at 10°C min⁻¹ up to 1000°C. The air reactivity of C/C composites was assessed from the weight loss curves obtained under isothermal conditions in the temperature range of 500 to 575°C for 4 h. The topography of the oxidized composites was examined by scanning electron microscopy. The results showed that pitch-cokes were more reactive than carbon fibres because the presence of QI particles increased their reactivity. With the increase of primary QI content in the pitches, C/C composites showed a higher percentage of carbon matrix, with a finer optical texture, fewer microcracks and less closed porosity. The air reactivity of the composites was affected by both chemical and physical factors, the extent of oxidation determining which of these exerted the greater influence. At low conversions the reactivity was decided by both QI content and the optical texture of the matrix. At high conversions the porosity of the composite was the determining factor.     

Evolution of chemistry and morphology during the carbonization and combustion of rice husk

Both fine carbon/silica and pure silica powders can be obtained by carbonization and combustion of rice husk under non-isothermal conditions, and the products can be used for preparation of high-quality ceramic materials. Studies on the morphology, chemical and physical characteristics of products were carried out by N₂-adsorptionmeter, SEM, XRD, FTIR, ICP-MS and EA. Results indicate that decreasing the heating rate increased the specific surface area, pore volume and pore diameter. At a heating rate of 5 °C/min, the specific surface areas of both the carbon/silica and pure silica powders were 261 and 235 m²/g, and the average pore diameters were 2.2 and 5.4 nm, respectively. The products obtained from various heating rates were all amorphous. Thermogravimetric analysis was employed to study the reaction characteristics during carbonization or combustion, indicating that decomposition process of rice husk could be divided into three temperature zones. This results of the study can also provide the important information on the recovery of biomass material from rice husk.     

Injection and stabilization of mesophase pitch in the fabrication of carbon-carbon composites. Part III: Mesophase stabilization at low temperatures and elevated oxidation pressures

Micrography and infrared spectroscopy were applied to explore microstructural stabilization of mesophase pitch at oxidation temperatures as low as 130 °C. AR mesophase pitch synthesized from naphthalene was drawn to rods and thick filaments with fine fibrous microstructures that coarsen upon carbonization without adequate stabilization. At 270 °C, the stabilization front advances rapidly to a depth of about 7 μm, after which no further growth is perceptible. At low temperatures, there is a time lag before a stabilized layer can be observed near the surface, but thereafter the stabilization front advances relatively rapidly. For longer oxidation times, the low-temperature stabilization depths can exceed those attained at higher temperatures. FTIR spectra confirmed chemical reactivity and the formation of oxygen-bearing functional groups even at the low oxidation temperatures. Oxidation under a moderate pressure of 0.7 MPa can be effective in raising the oxygen uptake and increasing the stabilization depths significantly. All evidences point to the advantageous use of lower oxidative temperatures: more effective penetration of stabilization depth, lessen destructive effects of over-oxidation, and potentially shorter processing times.     

Injection and stabilization of mesophase pitch in the fabrication of carbon-carbon composites. Part I. Injection process

The fabrication of carbon-carbon composites by injection of low viscosity mesophase pitch through a fiber preform followed by stabilization and carbonization was examined. The fully transformed mesophase MOMP and AR pitches were injected through either soft or rigidized disk preforms 35 mm thick and 68 mm in diameter. Injection provided good even filling of major flow channels and fiber bundles. Flow-induced fibrous microstructures were retained by quenching and preserved by stabilization upon carbonization. A second injection cycle was effective in filling voidage created by thermal densification. A third cycle was applied, but required severe injection conditions and provided only incremental improvement. The carbon-carbon composite reached a density of 1.8 g/cm³ after three injection cycles.     

Injection and stabilization of mesophase pitch in the fabrication of carbon-carbon composites: Part II. Stabilization process

In the fabrication of carbon-carbon composites by mesophase injection through a fiber preform, it is essential to stabilize the flow-induced microstructure in the flow channels and to prevent relaxation and exudation of the mesophase. Oxidation stabilization studies were conducted on preforms injected with the naphthalene-based AR mesophase pitch. Oxidation mass gain (OMG) curves at 170, 222, and 270 °C were generated for 60°-wedges cut from full size composite disks. The rates of OMG at 170 °C of first- and second-cycle injection wedges and full-size disks were comparable to those using as-spun filaments 30 μm in diameter, and particles sieved to 200 to 340 μm. The results suggest that oxygen is accessible deep into a mesophase matrix and the transport is facilitated by connected array of shrinkage cracks. Oxidation at 170 °C has strong advantage over higher oxidation temperatures by having a higher carbon yield and lower OMG threshold and thus oxidation time required for stabilization. The 60°-wedges could be stabilized at 170 °C after a 25 h oxidation with a 7.2% OMG and attaining a carbon yield above 85%.