A scanning electron microscope study of fractured and etched metallurgical coke surfaces

The object of this work was to attempt to link more closely coke strength and structure by establishing whether features visible on fracture surfaces could be identified with coke carbon textural constituents revealed either by polarized light microscopy of polished surfaces or by scanning electron microscopy of atomic oxygen-etched surfaces. The cokes used were produced in a laboratory furnace from coals covering the whole range or rank normally encountered in metallurgical coke production in the UK. Fracture surfaces were created by tensile fracture during diametral compression. In all three surfaces examined, the appearance of components derived from reactive coal constituents varied with the rank of the coal carbonized. A clear similarity was evident between features visible in the etched and fracture surfaces. The marked variation of fracture features imply that the textural composition of the coke carbon may make some contribution, as yet unquantified, to the variation in strength among cokes.     

The strength of industrial cokes: Part 4. The influence of carbonizing conditions on the tensile strength

The objective of this study was to ascertain if the observed differences in strength behaviour of blast-furnace and foundry cokes could be attributed to the different carbonizing conditions used in their production. Two coal blends, one being representative for blast-furnace coke production and the other for foundry coke production, were carbonized in a small-scale test oven using a wide range of heating conditions which included those used in the industrial production of the two types of coke. Coke tensile strengths were determined by the diametrical-compression test and a small-scale drum test was used to derive strength indices comparable to standard micum indices. The tensile strengths and material constants obtained by Weibull statistical analysis, when related to those drum-test indices which assess the resistance of coke to attrition and to corresponding data for equivalent commercial cokes, demonstrated that the cokes fell into two distinct sets according to the coal blend used. It was concluded that changes in coke strength caused by different carbonizing conditions could not account for the different strength behaviour of blast-furnace and foundry cokes. The alternative hypothesis that the nature of the coal blend is the predominant factor is supported by the correlations established for each of the coal blends.     

The strength of industrial cokes. 6. Further studies of the influence of coke breeze in a coal charge on tensile strength of coke

The objective of this investigation was to ascertain if there was any pattern in the dependence of the tensile strength of coke on the proportion and particle size of coke-breeze in an oven charge and to establish if it was possible to interpret the changes in tensile strength in terms of coke structural features. Using a small-scale oven in order to obtain the optimum in close control of the charge preparation and carbonization conditions, cokes were prepared from each of two coking coals blended with coke breeze. The tensile strength of these cokes was determined by the diametrical-compression test and some details of their porous nature were determined from density measurements, mercury porosimetry and optical microscopy. The results clearly demonstrate that the tensile strength of coke is, in general, systematically reduced with increasing breeze content of the oven charge, the more coarsely ground breeze leading to a greater reduction of the tensile strength at any level of breeze addition. But very finely ground breeze at relatively low levels of addition can lead to an improvement in the tensile strength. These changes correlate with variations in the apparent density and the total porosity and possibly also with the average pore size.     

The strength of industrial cokes. 7. Further studies of the influence of additives in a coke-oven charge on the tensile strength of coke

The objective of this investigation was to determine if the previously established dependence of the tensile strength of coke on the breeze content and particle size of coke breeze in the coke-oven charge was applicable to different types of breeze additives when used in a size range similar to that of commercial practice. Using a small-scale oven to obtain the desired close control of the charge preparation and carbonization conditions, cokes were prepared from a Yorkshire strongly-caking coal blended with either coke-oven breeze, petroleum-coke breeze, or silica sand. The tensile strength of the cokes was determined by the diametral-compression test and some details of their porous structure were obtained from density measurements and mercury pressure porosimetry. The results confirm that the tensile strength of coke varies systematically with the coke-oven breeze content of the oven charge, and in the present case, for a breeze of the particle size range used in commercial practice the tensile strength is increased at low additions and then progressively reduced at higher levels of addition. Different sources of coke-oven breeze behave in a similar manner and appear to act as an inert filler material. On the other hand petroleum-coke breeze additions progressively increase the coke tensile strength, the additive being bonded into the walls of the coke matrix. The changes in tensile strength are accompanied by systematic variations in apparent density and in porosity.     

The strength of industrial cokes. 5. Influence of coke breeze in a coal charge on tensile strength of coke

The purpose of this study was to determine the influence of different proportions and different particle sizes of coke breeze in a coke-oven charge on the tensile strength of the coke. The diametrical-compression test was used to determine the tensile strength of the coke produced in a 10-t test oven and the results obtained were considered in relation to the composition of the oven charge, the coke micum indices and to parameters describing the coke texture. It was established that breeze additions caused measurable but nonsystematic changes in the coke tensile strength and that decreasing the breeze particle size generally increased the coke tensile strength. These changes could not however be directly related to changes observed in the density, porosity, pore-wall thickness or mean pore size of the cokes. The previously established relations between micum indices and the tensile strength of foundry cokes were also found to be inapplicable. The conclusion was drawn that the behaviour described is associated with some, at present unestablished, factor of the blend composition, one possibility being the relative proportions and compatibility of the ‘binder’ and inert material acting through their influence on those aspects of the coke microstructure which control the coke breakage.     

Effect of low-volatile additives on the structure and strength of cokes

Blends of medium-volatile or high-volatile coals have been carbonized in a 7 kg oven with low-volatile coals (6–16% VM, dmmf). A comparison is made of the strength and structural properties of these cokes with those of the cokes made under corresponding conditions from the medium or high-volatile coals alone. With increasing levels of addition of the low-volatile coals the tensile strength of the blend cokes generally attains a maximum and then decreases. These strength changes are related to changes in porosity, pore-wall thickness and pore dimensions. Coals which display some degree of plasticity and which are weakly caking improve coke quality by altering the pore-structure due to the combined effects of decreasing the pore diameter and slightly increasing the wall thickness. Those additives which are non-caking act primarily as wall thickeners.     

The characterization of interfaces between textural components in metallurgical cokes

Six coals, representing the rank range normally encountered in commercial coking, were carbonized in a small oven to give dense cokes, of tensile strength comparable with that of good-quality blast-furnace coke. Interfaces between the different textural components in the cokes were studied by polarized-light microscopy. It proved possible to classify interfaces according to their perceived quality, to quantify their occurrence by point-counting and to calculate interface quality indices for the coke as a whole or for interfaces involving individual textural components. Interfaces between vitrinite-derived reactive coke components were superior to those involving inerts, but the inerts content of a coke did not have a marked influence on the coke interface quality index. The highest coke interface quality index was observed for the coke from the coal with the highest dilatation. No clear evidence of an influence of interface quality on coke tensile strength is apparent from the present data.     

Structure in metallurgical cokes and carbons as studied by etching with atomic oxygen and chromic acid

Anisotropie carbons and cokes exhibit an optical texture or micro-texture in the size range 0.5–300 μm in polished surfaces using optical microscopy. Structure within this optical texture can be studied as the topography created by etching surfaces with atomic oxygen and chromic acid. Atomic oxygen preferentially etches an isotropic carbon layer which exists between the grains of the fine-grained mozaics. Chromic acid oxidizes or etches selectively the surfaces of anisotropic carbon to create fissures parallel to basal plane orientation. Structural components within petroleum cokes, carbon fibres and carbon/carbon fibre composites are revealed. Chromic acid oxidizes isotropic components in metallurgi-cal cokes more slowly and so reveals the structure of cokes as prepared from co-carbonizations of coal with petroleum pitch. It is considered that these etching techniques augment our knowledge of internal structure within carbons and cokes and of considerations of strength and fracture in these materials.     

Influence of gas composition on the reactivity of cokes

The NSC reactivity test is often criticised for not being able to accurately predict the performance of cokes in the blast furnace. One explanation proposed for this inaccuracy is that the gas used in the NSC test, pure carbon dioxide, is different to the gas that coke is exposed to in blast furnaces, which is a complex mixture including carbon monoxide, carbon dioxide and nitrogen. The aim of this work was to see to what extent different cokes behaved differently during the NSC test under different gases.Nine Australian coals, used in coking blends, were selected to cover a wide range of rank, maceral composition and elemental composition of the mineral matter. These coals were coked and their relative reactivities in a series of gas mixtures were compared. The time for the reaction of the coke in a 30% CO₂/70% CO mixture was set to eight hours to give about the same weight loss as two hours exposure to 100% CO₂.The main conclusion of this study was that gas composition (using mixtures of CO, CO₂ and N₂) had little effect on the relative rate of gasification of cokes over a wide compositional range of gas and of coke (although of course the absolute reaction rate decreased with decreasing CO₂ levels). The previous studies that suggested changes in gas composition affect the relative reaction rate of different cokes were misleading because they performed the studies at constant burnoff time (2 h) rather than ensuring the cokes were reacted to about the same weight loss.Thus any differences between the behaviour of cokes in the NSC test and in the blast furnace are not due to differences in gas composition between the two.The CSR value was found to be a combination of strength and reactivity: for the data in this study, CSR was determined by a two-component fit involving CRI and the I600/10 index (the strength of the unreacted coke as measured by the CSR tumble test).     

Study of the reaction of cokes with KOH under nitrogen

Five cokes of increasing content of anisotropic carbon were prepared. Polished surfaces of these cokes were characterized by optical microscopy in terms of components of optical texture. These surfaces were reacted with KOH at 873, 1073 and 1273 K in an inert atmosphere for 2 h and the resultant topography monitored by scanning electron microscopy (SEM). The extent of potassium take-up by coke particles was measured and the diffusion of potassium was detected by EDAX. Microstrength testing was made on the cokes before and after reaction with the alkali. Coke reactivity measurements were obtained for untreated and treated cokes. Results indicate that in an inert atmosphere the alkali reacts preferentially on the prismatic edges of anisotropic carbon and that the rates of reaction increase with increasing temperature. Potassium is able to diffuse into the interior of the more anisotropic coke particles and this casues weakening of the coke. The reactivity measurements indicate that for the more anisotropic cokes the effect of potassium as a catalyst in the solution-loss reaction is more pronounced than for the least anisotropic coke. These conclusions suggest that metallurgical coke in the blast furnace in the presence of alkali materials can lose strength by direct reaction over and above considerations of gasification processes.     

Laboratory coal carbonization oven

A laboratory coal carbonization oven has been described which simulates the carbonization of coal in a commercial slot-type oven. Essentially a cylinder of packed, crushed coal is inserted at a controlled rate into a long furnace so that a plastic layer moves progressively along the cylinder. Widely varying coal charges and carbonization conditions can be employed. The tensile strength and pore structural data of the cokes produced under standard conditions lie within the range of values obtained for commercial cokes.     

Coal rank and coke reactivity

For a series of cokes prepared under identical carbonizing conditions it was shown that rates of reaction with carbon dioxide/nitrogen mixtures at about 1000°C were generally higher for the cokes prepared from coals of above 30% volatile matter. The reaction rates of cokes prepared from certain Durham coals were generally higher than anticipated. Gasification of cokes prepared from certain Durham coals were generally higher than anticipated. Gasification of the cokes resulted in loss of strength, decrease in apparent density, enlargement of pores and reduction of pore-wall thickness. It appeared that burn-off was primarily associated mineral constituents of the coke ash upon gasification rates was detected. A tentative relation was derived between gasification rates and the ratio of pore-wall thickness to pore diameter of the cokes. In turn, this latter ratio appeared to bear some relation to the oxygen content of the coal. The majority of the parameters studied were measured by established techniques. Porosity was determined by mercury pressure porosimetry and the Quantimet 720 automatic image analysis microscope was employed for structural studies. The accuracy of the measurement of pore and pore-wall dimensions was approximately ± 2%.     

Catalytic graphitization of cokes by indigeneous mineral matter

Indigeneous mineral matter in coals acts catalytically towards graphitization during heat treatment of coals to 2273 K. Nineteen coals of a wide range of rank were demineralized by acid extraction. Original and demineralized coals were carbonized in the range 1073–2273 K, and the resulting cokes examined by optical microscopy, X-ray diffraction and phase-contrast high resolution electron microscopy. Optical microscopy indicated the extent of formation of anisotropic carbon in the resultant cokes. The (002) X-ray diffraction profiles indicated three types of catalytic effect, for which electron microscopy demonstrated different crystallite structures and interrelations. The importance of catalytic graphitization in metallurgical cokes in relation to their strength and reactivity is discussed.     

Examination of some effects of dry cooling on coke quality

A series of coals were carbonized, on the 250 kg scale under standardized conditions, to provide both dry-cooled and wet-quenched cokes which were subsequently subjected to reactivity and strength testing. The data from the tests of reactivity to CO₂ at ≈1000 °C support the view that dry coke cooling leads to lower reactivity, but examination of the porous structure in the pore size range > 5.45 μm and of the optical anisotropy of the coke carbon revealed no changes to account for this effect. Although the micum test indices were sometimes improved by dry coke cooling, the differences were not statistically significant. On the other hand, there was clear evidence of increased coke tensile strength. The effect of dry coke cooling on coke properties appears to be sufficient to exert some influence on the blast furnace coke rate and thereby on the economy of the dry-cooling process.     

石墨碎在电极生产中的作用

通过石墨碎、大庆石油焦、锦州石油焦的对比试验,分析了石墨碎的性能,并通过生产试验,分析了石墨电极生产中加入石墨碎对生产及产品的影响。石墨碎具有真密度高、体积密度大,电阻率、CTE偏低,振实密度、颗粒强度大等优点。在石墨电极生产中加入一定的石墨碎可以提高产品的体积密度、强度,降低电阻率等。     

Carbonization of coal blends: mesophase formation and coke properties

Laboratory investigations of strength of cokes from blends of coals incorporating pitch were supported by 7 kg trials. The stronger cokes showed a greater interaction between coal and pitch to produce an interface component of anisotropic mozaics which is relatively resistant to crack propagation. The process whereby coal is transformed into coke includes the formation of a fluid zone in which develop nematic liquid crystals and anisotropic carbon which is an essential component of metallurgical coke. Strength, thermal and oxidation resistance of coke can be discussed in terms of the size and shape of the anisotropic carbon which constitutes the optical texture of pore-wall material of coke. Coals of different rank form cokes with different optical textures. Blending procedures of non-caking, caking and coking coals involve the interactions of components of the blend to form mesophase and optical texture. Petroleum pitches used as additives are effective in modifying the carbonization process because of an ability to participate in hydrogen transfer reactions.     

添加炭素物料改善焦炭性能的研究

通过向炼焦配煤中添加石油焦、人造石墨和天然石墨并炼焦处理，研究了添加炭素物料对焦炭性能的影响，结果发现，添加少量炭素物料有效地提高了焦炭强度并降低了焦炭的反应性。     

焦炭颗粒的粒度分布及其微观结构研究

焦炭颗粒是生产碳石墨制品的主要原料，它的粒度组成、分布及其微观结构不仅对碳石墨制品的机械性能和理化性能有一定的影响，而且还直接影响到各生产工序的成品率．为此，主要对粉碎后几种焦炭颗粒的粒度组成、分布及其微观结构进行了研究．并通过分析，确立了焦炭颗粒的粒度组成及其分布规律与粉碎方式和焦炭强度之间的内在关系．     

Composition of pore-wall material in metal-lurgical coke: Considerations of strength,gasification and thermal stress

The optical texture of metallurgical cokes consists of anisotropic carbon made up of mozaics, 0.5–10 μm in size of flow-type anisotropy, 10–60 μm in size, as well as inert and isotropic material. Cokes from different coal sources possess optical textures which are different, being composed of different extents of the above components. The study examines the optical texture of polished surfaces of cokes and relates changes in surface topography caused by gasification by carbon dioxide at 1173 K, by heat treatment to 2073 k and by etching with atomic oxygen at 293 k to the optical texture. The results support a model to explain the strength of coke and its resistance to breakage caused by gasification, mechanical and thermal stresses, in terms of the size, orientation and bonding of the varied components which constitute the composite structure of coke material.     

Tensile properties of carbon filled liquid crystal polymer composites

Electrically and thermally conductive resins can be produced by adding carbon fillers. Mechanical properties such as tensile modulus, ultimate tensile strength, and strain at ultimate tensile strength are vital to the composite performance in fuel cell bipolar plate applications. This research focused on performing compounding runs followed by injection molding and tensile testing of carbon filled Vectra A950RX liquid crystal polymer composites. The four carbon fillers investigated included an electrically conductive carbon black, thermocarb synthetic graphite particles, and two carbon fibers (Fortafil 243 and Panex 30). For each different filler type, resins were produced and tested that contained varying amounts of these single carbon fillers. The carbon fiber samples exhibited superior tensile properties, with a large increase in tensile modulus over the base polymer, and very low drop in the ultimate tensile strength as the filler volume fraction was increased. The strain at the ultimate tensile strength was least affected by the addition of the Panex carbon fiber but was significantly affected by the Fortafil carbon fiber. In general, composites containing synthetic graphite did not perform as well as carbon fiber composites. Carbon black composites exhibited poor tensile properties. POLYM. COMPOS., 29:15–21, 2008. © 2007 Society of Plastics Engineers