Étude des phénomènes de mouillabilité du carbone par le brai liquide

One of the processes used in the manufacture of carbon/carbon composites makes use of impregnation with pitch of a multidirectional structure of carbon rods made of carbon fibres at high temperature followed by carbonization under high pressure. A densification of the composite is obtained by repeated impregnations.Since the mechanical properties of the composites must likely depend on the quality of the interface formed between the carbon rod and the liquid pitch matrix, the wetting properties of pitches of various origins and properties (Table 1) were studied for several carbon rods (Table 2). A tensiometric method based on the weight of pitch lifted during immersion of the carbon rod at 350°C was used (Fig. 1).Measurements of the surface energy of the pitches in the liquid state at 350°C (Table 3) and in the solid state at room temperature (Table 4) show that the surface energy is practically independent of the origin of the pitch and that the surface polarity of the pitch is negligible. On the contrary, the values of the contact angle at 350°C is higher for the petroleum pitch No. 1 than for the coal tar pitches (Table 5).The wettability criteria, i.e. the spreading coefficient S and the wetting tension τ, derived from the measured surface energy and contact angle, confirm the lower wetting ability of the petroleum pitch (Fig. 2). These criteria may explain why the densification process (number of impregnations and carbonization cycles necessary to reach an apparent density of the composite of 1.90) is much more difficult with petroleum pitch. On the contrary, the adhesion criterion factor, expressed as the reversible energy of adhesion between the liquid and the solid at 350°C, has the same value whatever the origin of the pitch. Since the degree of adhesion might influence the quality of the carbon/carbon interface in the composite, the same value of the adhesion criterion factor may explain why all composites, at equivalent density, show about the same compression and torsion strengths.The difference between the wettability and adhesion for the pitches of different origins is due to the difference in the spreading pressure π; this quantity measures the decrease of the surface energy of the carbon rod resulting from the adsorption of the pitch vapor. The calculations reveal that, whatever the surface energy of the carbon rod, the petroleum pitch leads to a larger reduction of the surface energy of the solid than the coal tar pitches (Fig. 3).The wettability and adhesion criteria adopted in this study seem to (at least to a first approximation) explain the dependence of the mechanical properties of the carbon/carbon composites on the type of pitch and on the processing conditions.     

Correlations between ability of pitch to penetrate coke and the physical characteristics of prebaked anodes for the aluminium industry

The nature of the interaction between coke and pitch is basic to the final properties of anodes for the aluminium melting industry. One of the significant properties of pitch which contribute to the quality of this binding is its ability to wet coke. The investigations reported here indicate the optimum experimental conditions for the use of an automatic apparatus that monitors pitch penetration into a coke bed. The penetration test described can be used to select pitches with good affinity for petroleum coke and to correlate this quality with the physical properties of electrodes produced therefrom. A particularly important conclusion is that the test suggests the suitability of certain pitches which would not satisfy the usual selection criteria. The temperature-dependent ability of a pitch to penetrate a coke bed, in conjunction with the traditional criteria, assists in the selection of binder pitches used in the aluminium industry.     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

Influence of granular carbons on pitch properties

This paper deals with the study of the variation of properties of four pitches (a commercial impregnating coal tar pitch, an air-blown and two thermally treated pitches) when mixed with four granular carbons (anthracite, graphite, green petroleum coke and foundry coke). As a first step, optical microscopy was used to determine the distribution of the pitch among the granular carbons. The anthracite seems to attract the primary quinoline insolubles present in the commercial and thermally treated pitches. This allows the mesophase spheres to coalesce at unusually low temperatures during the mixing process. In general, the toluene insoluble content of the pitch showed a significant increase after mixing with the granular carbons. This is an indication of the interactions between the different granular carbons and some compounds present in the pitches. Analytical techniques like size exclusion chromatography and differential scanning calorimetric analysis were used in order to obtain information about the characteristics of the components of the pitches that interact with the different granular carbons and their effect on pitch properties. Graphite seems to interact preferentially with the larger molecules whereas the green petroleum coke acts on a wider molecular range.     

SEM study of binder coke in electrode carbon

As part of a study on the use of coal-tar pitches as binders in electrode carbons for the aluminium industry, the object of the present work was to attempt to identify textural components in electrode binder cokes. Accordingly, four experimental carbons, made using the same petroleum coke as filler and four coal-tar pitches of differing characteristics as binders, were examined in a scanning electron microscope (SEM) after embedding in resin, polishing and etching in atomic oxygen. Binder cokes could be distinguished from the filler particles and could be characterized in terms of the content of three components, termed lamellar, intermediate and granular. The textural composition of the binder cokes was dependent upon the character of the pitch and the type of quinoline-insoluble components present. Pitch cokes, made by carbonizing the pitches alone, differed markedly from the corresponding binder cokes. The findings are considered in terms of current ideas on pitch carbonization.     

Modification of petroleum coke by different additives and the impact on anode properties

Anodes, which provide the carbon required for aluminum production, are made from dry aggregates (petroleum coke, rejected anodes, and butts) with coal tar pitch as the binder. Good quality anodes require good interaction between coke and pitch, and this relies on good wetting properties. The objectives of this work are to analyze the wetting properties of four different cokes with and without modification using an additive and to test the effect of the modified coke on anode properties. A FTIR study was done to identify functional groups in non‐modified and modified coke samples since they play an important role on coke‐pitch interactions. The wetting tests were done using the sessile‐drop method to measure the contact angle between coke and pitch. The results showed that the additive improved the wettability of all four cokes by pitch. The least wettable coke was chosen to produce anodes. For anode production, the entire dry aggregate is modified. The additive was mixed with the dry aggregate using two different approaches (one day earlier and 5 min before mixing). The anodes were characterized before and after baking. The early treatment with the additive was found to be better for the modification of dry aggregate.

     

Interaction effects between the constituents of carbon artefacts during graphitisation

A crystallographic study, using X-ray diffraction techniques, has been made of the interaction effects between the constituents of coke-binder artefacts when heat-treated to graphitising temperatures. It is shown that petroleum and pitch cokes graphitise to a greater extent separately than when combined in petroleum coke/pitch binder artefacts, but for artefacts based entirely on either petroleum or pitch, this effect of the binder in retarding graphitisation of the grist coke is very much less.     

铝电解槽用无烟煤基石墨化阴极材料的初步研究

选取优质电煅无烟煤,分别配以一定比例的石油焦和沥青焦作为骨料,与煤沥青混合后按照模压成型、焙烧、高压浸渍、二次焙烧和石墨化等常规炭素制品生产工艺流程制备石墨化阴极材料试样。考察了无烟煤和3种少灰料以不同配比混合制成的试样在焙烧和石墨化过程中的尺寸变化及理化性能变化规律,并通过对4种以单一原料制备的试样的理化性能分析,探讨了原料种类对试样性能的影响。结果表明,以无烟煤为主要原料,配以一定比例的少灰料作为骨料,通过适当的炭素工艺制备的石墨化阴极材料试样,其常规理化性能可以满足大电流铝电解槽用阴极材料的要求。     

The effect of the substrate on pitch wetting behaviour

The wetting behaviour of a petroleum pitch (modified with a surfactant) and a binder coal-tar pitch was studied using different substrates. The results show that both the pitch and the substrate have a significant influence on wetting behaviour, and consequently, on their mutual interactions during the mixing stage. Low values of surface tension and viscosity in the pitches lead to lower wetting temperatures. It was found that with petroleum coke and magnesia as substrates, the wetting occurs at lower temperatures than with graphite and carbon black for all pitches. Moreover, experiments carried out with amorphous and crystalline alumina revealed that the crystalline order affects the wetting behaviour considerably. Thus, whereas the pitch wets the corundum (crystallized alumina), it does not wet the amorphous alumina (basic, acid and neutral alumina).     

Pitch and petroleum coke additions to coke oven charges

Several pitch materials and a petroleum coke were added to coke oven charges in an attempt to make good metallurgical coke from Canadian coal of poor coking quality. Coal and petroleum pitches were added to a low fluid western Canadian coal of medium volatile bituminous rank, and the blends coked in a technical-scale moveable wall test oven having a 230-kg charge capacity. Pitches improved coke tumble test indices, the principal coke quality parameter related to blast furnace performance. Varying levels of petroleum coke were added to an eastern Canadian coal of high volatile bituminous rank, and the blends, some partially briquetted, were carbonized in a test oven. Tumble indices of coke from the partially briquetted charges approached an acceptable level. These investigations confirm that petroleum products as well as coal derivative can play a useful part in the production of a metallurgical strength coke from poor or non-coking coals.     

Influence of the coke filler on the carcinogenicity of pitch–coke mixtures on carbonization

The emissions of benzo[a]pyrene at different temperatures and its concentration in the exhaust gases are measured in laboratory experiments on the carbonization (at temperatures up to 850°C) of coalpitch and petroleum-pitch binders and their mixtures with roasted petroleum and pitch coke. These pitch–coke mixtures are similar in composition to the anode mass used in aluminum production. The experiments confirm that the total benzo[a]pyrene emissions are much greater in the carbonization of petroleum pitch produced by cracking (T _so = 100°C) than for electrode pitch (T _so = 89°C) and other coal pitch. In most experiments, the benzo[a]pyrene emissions in the carbonization of pitch–coke mixtures is markedly less than for individual binder pitches. It is found that the benzo[a]pyrene emissions in the carbonization of a mixture based on pitch coke are much less than for a mixture based on petroleum coke in the high-temperature region that presents the greatest environmental hazard.     

A novel method to obtain a petroleum-derived mesophase pitch suitable as carbon fibre precursor

This paper studies a novel method for the preparation of mesophase pitches suitable as carbon fibre precursors. A series of thermally treated petroleum pitches with mesophase contents ranging from 10.8 to 52.2 vol.% was obtained from pitch A-240. Separation of the phases was initially attempted by hot filtration, a suitable method for separating the phases in thermally treated coal-tar pitches. Although filtration failed for the petroleum samples, the behaviour observed led to the development of a new separation method that consists in the sedimentation of the mesophase. This method, after optimisation, yielded pitches with mesophase contents up to 97 vol.%, which were easily spun into carbon fibres of reasonable mechanical properties.     

复合粘结剂炭素材料性能研究

用自制凝胶一沥青作复合粘结剂制备了炭素材料。通过测定不同配方、焙烧温度下试样的物理性能,认为9~#配方试样具有较好的导电性能和较高的抗压强度,沥青用量只有20%,明显低于传统炭素材料沥青用量。结果表明,凝胶一沥青复合粘结剂与石油焦粘结性能好,改变了传统的热压成型工艺。     

Influence of primary QI and particulate matter on pitch carbonizations

The carbonization behaviour of coal-tar and petroleum pitches is influenced by the presence of particulate matter in the pitch. Several types of particulate matter consisting of carbon blacks of different oxygen contents and degrees of agglomeration and silica with hydrophobic and hydrophilic surfaces were added to pitches. Particle sizes were less than 100 nm in diameter. The influence on optical texture of coke structure was most pronounced for the agglomerated carbon blacks which trapped pitch in inter-particle voids creating an isotropic carbon at low wt % additions. The non-agglomerated hydrophobic silica progressively reduced the size of anisotropy with additions. The hydrophilic silica caused intermediate effects. Surface activity of additives influences carbonization chemistry. Reactivities of cokes to carbon dioxide (k/s⁻¹) were not affected by structural changes but coke microstrengths were very dependent upon size of agglomeration of carbon black additives.     

Rheological properties of carbon mixes at very low shear rates using a capillary rheometer—III

A capillary rheometer has been used to determine the rheological properties of carbon mixes consisting of petroleum coke as filler and coal tar pitch as binder. It is shown that carbon mixes behave as Bingham materials with definite yield stresses. The yield stress was found to be a general property of all carbon mixes and its value is independent of the size of the capillary die. It was also seen that extrusion at low shear rates through big diameter capillaries results in slipflow. The slipflow occurs when the applied stress is somewhat below the yield stress, the material then extrudes without the formation of a core which otherwise would cause cracks in the product after baking. This explains why big diameter rods are generally extruded at very low speeds in usual manufacturing process. The modified Buckingham-Reiner equation has been applied to the case of slipflow and the values of yield stress and plastic viscosity calculated. These values agree well with those obtained from the consistency curve.     

沥青粘结剂产炭率对制品性能的影响

研究了粘结剂沥青产炭率与块状炭制品材料性能的关系,拟通过提高粘结剂沥青产炭率的方法改善炭制品的性质。实验采用比目前工业沥青粘结剂产炭率更高的沥青作为粘结剂,经过混捏、成型和焙烧制成炭制品。研究发现,采用产炭率高的粘结剂可以得到性能较好的产品,但对于强度来说,过高产炭率的粘结剂并不总是正面影响的,应考虑到粘结剂中β组分的含量。     

均四甲苯改性沥青组成与性能的关系

考察了不同压力体系中均四甲苯改性沥青的ＴＳ组分和ＰＩ组分与沥青软化点,焦化值及粘度三种性能参数之间相互关系,发现同一压力体系中所得沥青ＴＳ组分和ＰＩ组分与三种性能参数之间存在良好的线性关系;不同压力体系导致沥青化点波动较大,而焦化值变化相对较小。比较分析了三种压力体系中所得沥青的组成－性能关系。半封闭体系下的改性沥青,其ＴＳ组分和ＰＩ组分对沥青性能的影响较大。通过这些组成－性能关系。可以实现沥青的     

Sintering properties of composites consisting of carbon filler and binder

The sintering properties of composites consisting of coke and coal pitch are considered. The coke yield from pitch cannot be used to assess the sintering properties. The increase in coke yield from the pitch in the presence of filler is found to be correlated with increase in sintering properties and strength of the composite.     

Structure and carbonization properties of pitches produced catalytically from aromatic hydrocarbons with

Carbonization properties of pitches synthesized from some aromatic hydrocarbons by the aid of were studied under atmospheric 1.1 and 3.1 MPa pressures. The highest coke yields obtained under atmospheric pressure and 3.1 MPa were 64% and 85%, respectively, both of which were observed with anthracene pitch. Pyrene pitch exhibited a low coke yield of 37% under atmospheric pressure, but as high as 85% under 3.1 MPa.The pitches were revealed with ¹H-NMR and FD-MS to consist essentially of oligomers of starting aromatic rings such as dimers, trimers, and tetramers. The oligomers carried significant amounts of naphthenic hydrogens, which provide their low softening point and enable the development of an anisotropic flow texture when the pitch was carbonized. The carbonization scheme is discussed in relation to the coke yield.     

Carbonization and liquid-crystal (mesophase) development. 22. Micro-strength and optical textures of cokes from coal-pitch co-carbonizations

This study examines the micro-strength and optical textures of a laboratory coke from a base-blend of Freyming and Pocahontas coal (wt ratio, 1:1) and of cokes from the co-carbonization of the blend, with each of five petroleum pitches in various proportions. Coke pieces, 212–600 μm, from the micro-strength test are assessed in terms of origin and propagation of cracks induced by the test. Always, the addition of pitch to the base-blend improves the strength of the resultant cokes, the pitches behaving differently. A qualitative, subjective appraisal of results indicates that increases in coke strength are associated with relative abilities of pitches to interact with the coals to produce a fluid phase, of solution of coal in pitch, which gives an ‘intermediate’ coke with an optical texture of mozaics. This intermediate coke strengthens the bonding at interfaces. Cracks originate predominantly from the shrinkage cracks in the domains of Pocahontas coke. Mozaic structures tend to resist crack propagation. The coal/pitch system may flow around coal particles so containing incipient crack formation in resultant coke particles.