Carbonization and liquid-crystal (mesophase)

development.
22. Micro-strength and optical textures of
cokes from coal-pitch co-carbonizations

Steve Ragan and Harry Marsh

Northern Carbon Research Laboratories, School of Chemistry, University of Newcastle
upon Tyne, Newcastle upon Tyne NE1 7RU, UK
(Received 16 April 1980; revised 28 November 1980)

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 :I ) and of cokes from the co-carbonization of the blend, with
each of five petroleum pitches in various proportions. Coke pieces, 212-600pm, 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.

Reduced availability and high costs of prime coking coals EXPERIMENTAL

on a world-wide scale have increased the importance of
Materials used
the use of coking additives i.e. carbonaceous materials
other than coal, in the manufacture of metallurgical coke. Coals: Freyming NCB 602/702 high-volatile, weakly
The recent rise of the Japanese iron and steel making caking, International Rank 721; Pocahontas NCB
industries to world-wide pre-eminence has promoted 204/301a International Rank 334/434.
interest in their coke-making techniques which use such Petroleum Pitches: A, B, C (supplied by industry);
additives. petroleum pitch A240, Ashland Petroleum Company;
Petroleum pitch and heavy oils have been used as petroleum pitch A170, Ashland Petroleum Company.
additives in recent years1,2 but few fundamental studies of Details of co-carbonization blends are in Table 1.
mechanisms of modification to cokes by these additives
are reported 3 - ’ . This study comments upon the micro- Curbonization und procedure

structure of cokes from a binary blend of coals with pitch Coals and pitches were ground < 250 pm (BS 60 mesh).
utilizing the characteristics of pitch co-carbonizations in The base-blend of coals for pitch additions was (1:1)
assessments of metallurgical coke strength’. The influence Freyming:Pocahontas.
of porosity upon the strength of coke is well-documented The blends were carbonized under nitrogen in an open
(Patrick et ~1.~). Little has been reported upon the boat. in a Carbolite horizontal tube-furnace to 1273 K
influence of the micro-structure of the pore-wall material
of coke upon the strength and fracture mechanics of coke.
In this paper observed influences of micro-structure of
Tab/e I Blend compositions of cokes from co-carbonizations
cokes upon crack propagation in these cokes are
discussed. Coal blend Percentage pitch addition
It is stressed that the cokes were made on a laboratory Freyming: Pocahontas 5% 10% 15% 20% Pitch type
scale. Changes in microstrength are observed and these
changes are discussed relative to differences in optical 50:50
((1 :l)base blend) - - - - -
textures of cokes from blends incorporating pitch. 1 : 1 base blend J J J J A
Mechanisms by which strength in these cokes is improved 1 : 1 base blend J J J J B
are also considered. It is hoped that some of what is 1 : 1 base blend J J J J C
described here may find relevance in discussions of up- 1 : 1 base blend J J - - A240
1 : 1 base blend J J - - A170
grading of coke quality on the industrial scale.
0016- 2361/81/060522-O7$2.00
@ 1981 IPC Business Press

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 Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

Table 2 Mean % charge retained on size analysis after micro-strength observed in the specimens were recorded by colour photo-
determinations
micrography, the colours being produced by use of a half-
Concentration and Micro-strength indicesa
wave retarder plate placed in the beam path of the light
type of added pitch (96) R2 R3
between the specimen and analyser.

50:50 Base blend 17.5 80.8

RESULTS AND DISCUSSION
Pitch A 5% 26.8 70.5
10% 34.8 62.6 Micro-strength indices
15% 37.6 59.6
20% 42.1 56.2
Micro-strength data for cokes from the base-blend plus
pitch are in Table 2. Additions of petroleum pitches Al 70
Pitch 0 5% 34.8 62.2
10%
and A240 are limited to 5’y0 and lo’>;, due to excessive
36.4 61.2
15% 37.9 59.0 frothing of the sample during carbonization. The micro-
20% 43.9 53.8 strengths of resultant cokes can be listed (in increasing
Pitch C 5% 34.6 60.1
order) as follows:
10% 39.6 56.9
15% 43.4 52.7 5”,, pitch /o()0 pitch 20~fo pitch
20% 46.9 50.7 addition addition addition
Ashland A240 5% 41.5 54.3
,I ,I
10% 41.9 54.0 A A (weakest) A
Ashland A170 5% 35.2 61.5 B B B
,, I,
10% 44.5 53.5 C C c
A170 A240 (Ashland)
a R2,212-600 pm; R3, <212pm
A240 A 170 (Ashland) (strongest)

Comparison of micro-strength indices of cokes from

(IOOOT) at 4 K mini, soak time of 30 min and cooled the coal:coal blend without pitch with those of the
under nitrogen. coal:coal:pitch blends (Table 2) shows that, the blends
containing pitch produce ‘stronger’ coke in terms of the
Micro-strength procedure micro-strength indices. The Ashland A 170, A240 pitches,
This apparatus assesses the ‘strength’ of coke by in the blends, produce stronger cokes than pitches A, B, C.
rotating two charges of coke (2 g), in triplicate, each in a These pitches for all levels of addition increase coke
separate cylinder, for 800 revolutions at a speed of 25 rev strength in that order.
mini ‘. Coke size is 1.2 mm-600 pm (1425 BS mesh).
The cylinders are stainless steel, length 305 mm, internal Opticul textures of’ cokes jPom coal und pitch
diameter 25.4 mm sealed by steel dust caps and each The carbonization of the Freyming:Pocahontas blend
containing 12 steel ball-bearings 8 mm diameter. These gives a coke from the Freyming coal containing isotropic
cylinders plus charged coke are rotated around their short material and fine-grained mozaics (0.5. 1.5 pm diameter,
axis by an electrically driven holding frame. The speed of Tuble 3). Coke from the Pocahontas coal contains
the rotation is such that the coke charge and ball-bearings isotropic material, tine- and coarse-grained mozaics and
fall the full length of the cylinders. domains (Tuble 3). Freyming coal contains * 10% of
The products of broken coke are collected on a 600 pm mozaics. The interfaces between these cokes are distinct
sieve (BS 25 mesh), R, index, below which are a 212 pm with no evidence of a common fused state having existed
sieve (BS 72 mesh), R, index, and a tray to collect the fines at the interface. It is thus quite easy to identify, in the
(R3 index). This set of sieves is mechanically shaken for optical microscope, the origin of the coke types in the
three minutes and the coke retained on the sieves and tray composite coke from this blend of coals.
is weighed. Each size fraction is expressed as a percentage
of initial weight ofcharge. For these cokes, only R, and R,
indices are reported. Tab/e3 Classification of optical texture in cokes

Assessment oj’optical texture Fine-grained mozaics (Mf) 0.5-l .5 Mm in diameter

The size fractions of coke from the micro-strength test Mediumgrained mozaics (Mm) 1.5-5 Mm in diameter
were assessed for optical texture by qualitative visual Coarse-grained mozaics (MC) 5-l 0 pm diameter
examination using a Vickers M41 reflected polarized light
Supra-mozaic (SM) Area of mosaic where car-
optical microscope.
bon layer planes are orien-
We report the subjective assessment of quite major tated in a similar direction
changes in optical texture which are distinct because of giving an isochromatic
easily recognisable differences in the optical textures of appearance , overa II
cokes from the coal, the pitch and the coal/pitch systems. Medium-flow anisotropy (MFA) <30 Mm in length; <5 urn
At this stage we are not reporting quantitative assess- in width
ments of optical texture with reliable statistical analyses. Coarse-flow anisotropy (CF) <&I >30 urn in length;
The size fractions, i.e. > 600 /*m, > 212 lrn, < 212 pm <lO >5 pm in width
were mounted in polyester resin blocks before being given Flow domain anisotropy >60 pm in length; >lO pm
(FD)
a high polish, necessary for good reflectivity, by means of elongated in width
Metaserv polishing apparatus using a range of alumina
Domains >fX Frn in diameter
powders. Typical micro-texture and fracture behaviour

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Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

Figure 7 Optical micrograph of coke prepared from base blend
with 5% pitch A. Position D shows isotropic coke from Freyming
coal, Position E shows fine- and medium-grained mozaics charac-
teristic of pitch coke A; Position F shows shrinkage cracks in do-
mains of Pocahontas coke
Figure3 Optical micrograph of coke prepared from base blend
with 5% pitch A. Position H shows interface between coke from
pitch A and isotropic coke (Freyming Coal), where rosettes have
penetrated into the isotropic coke

figure 4 Optical micrograph of coke prepared from base blend

with 10% pitch A. Position I illustrates the formation of an area
Figure 2 Optical micrograph of coke prepared from base blend of finegrainad mozaics possibly holding together two coke pieces
with 5% pitch A. Position G shows anisotropic rosette structures
of pitch A

Petroleum pitch A gives a coke made up of fine- and

medium-grained mozaics (Tuhle 3) the optical texture
showing anisotropic rosette structure$. Petroleum pitch
B gives a coke with a larger sized optical texture, coarse-
grained mozaics and coarse-flow anisotropy (Table 3).
Petroleum pitch C gives a coke containing two distinct
types of optical texture, namely medium-grained mozaics
associated with rosettes and coarse-flow anisotropy wi-
thout rosettes’. The Ashland Al 70 and A240 pitches gave
cokes having the largest of optical textures of flow domain
anisotropy (>60 pm in length: > IO pm in width and
isometric domains, >60 pm in diameter, Table 3).
Cokes from the blends of coal/coal/pitch contained
optical textures which could not be assigned clearly to the
coal or pitch. These optical textures must have arisen from
a fluid phase containing pitch and coal substance. In most
cokes, these new optical textures exist at interfacial
Figure 5 Optical micrograph of coke prepared from base blend
positions, and are termed ‘intermediate optical textures’.
with 15% pitch B. Position J shows an irregular interface of inter-
Fiyures I-16 are optical micrographs of polished mediate optical texture between isotropic coke (Freyming Coal)
surfaces of cokes recovered from the micro-strength and coke from the unmodified pitch

524 FUEL, 1981, Vol 60, June

 Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

which in turn are bonded to the domains of Pocahontas

coke, showing shrinkage cracks, Position F. Figure 2,
Position G, shows an anisotropic rosette in coke from
pitch A with Figure 3, Position H showing that several of
these rosettes have interlocked or keyed into the coke
from the Freyming coal. This is indicative that the coal,
although remaining isotropic, has softened sufficiently to
allow the rosette structures from the pitch to key onto the
coal particle interface. Figure 4, Position 1 illustrates the
formation of an intermediate optical texture of tine-
grained mozaics which may have formed from the in-
teraction of Freyming coal and pitch A. It appears to be
holding together two pieces of Freyming coke. In the
absence of rosettes it is impossible to monitor the depth of
interaction between the two cokes.

Base-blend with pitch B

Figures 5 and 6 are of polished surfaces of cokes of
Figure 6 Optical micrograph of coke prepared from base blend coal/coal/pitch B blend. Figure 5 illustrates the point that
with 20% pitch B, HTT 1273 K, 4 K min-l, 30 min soak period.
Position K shows the interface between domain (Pocahontas Coal)
and intermediate coke, Position L. A shrinkage crack from the
Pocahontas coke, Position M, passes into the intermediate coke and
terminates in the mozaic

Figure 8 Optical micrograph of coke prepared from base blend

with 10% pitch C. Position N shows isotropic coke (Freyming Coal).
Position 0 shows a domain of Pocahontas coke incorporated into
the intermediate coke. Position P is of intermediate coke

Figure 7 Optical micrograph of coke prepared from base blend

with 5% pitch C. Position Q shows interface between isotropic coke
(Freyming Coal) and coke from the pitch

apparatus and are sized 212-600 pm. As the purpose of

this paper is to give general indications of how the
strength of cokes is increased by pitch additions, these
micrographs are selected from many to illustrate those
structural aspects of optical texture which may possibly
contribute to observed changes in the micro-strength of
coke.
As Figures l-16 are of broken fragments attention is
given to the interfacial position and positions within the
optical texture of possible cracks (width > 1 pm) or
microcracks (width < 1 pm) in the cokes. There are
common features in cokes from all systems.

Base-blencl with pitch A

Figuresl~l are of polished surfaces of cokes of
coal/coal/pitch A blend. Figure I shows isotropic coke Figure9 Optical micrograph of coke prepared from base blend
from Freyming coal (Position D) bonded to the pitch- with 10% pitch A240. Note extensive development of fine-grained
coke, Position E, of fine- and medium-grained mozaics, mozaic and the absence of unmodified pitch coke

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Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

Bus+blend with pitch C

Figure 7, Position Q shows an interface between the
isotropic Freyming coke and the intermediate optical
texture as well as the general ‘interlocking’ of isotropic
coke particles by intermediate coke, to the left of Position
Q.
Figure 8 shows that Pocahontas coke, Position 0, may
become incorporated into the intermediate coke of line-
grained mozaics formed from Freyming coal and pitch C,
Position P, with Position N again showing the interface
between Freyming coke and intermediate coke with
penetration of the rosettes into the Freyming coke.

Buse-blend oith Ashlund A170, A240 pitch

In cokes using the 5% and 10% additions of these
pitches to the blend, it was not possible to identify any
pitch coke. Only the intermediate coke of fine-grained
mozaics could be found, as shown in Figure 9. Both the
Figure 10 Optical micrograph of coke prepared from Freyming:
Pocahontas base-blend (1 :I ). Position Y shows a micro-crack with
zig-zag path in coarsegrained mozaics

Figure 12 Optical micrograph of coke prepared from base blend

with 15% pitch A. Position R shows a crack curving round a pore
Figure I? Optical micrograph of coke prepared from base blend. in a domain of Pocahontas coke before extending into isotropic
Position V shows a crack encountering a pore, and continuing at a Freyming coke, Position S
position opposite its entry rather than being stopped by the pore

in this coke (5O’jb pitch B) it is rare to find pitch B coke.

The pitch appears to have been modified by solution in
coal to yield on carbonization an intermediate optical
texture. Position J is the interface between the isotropic
coke (Freyming) and the coke of intermediate texture
from coal/pitch interaction. This intermediate coke has an
optical texture of fine-grained with some medium-grained
mozaics. The coarse-grained mozaics and coarse-flow
anisotropy of coke from Pitch B are not observed. The
interface, Position J, is not sharp but is irregular showing
the various extents of penetration of the pitch into the
coal. In Figure 6, Position K is the relatively sharp
interface between the Pocahontas coke and coke from the
pitch/Freyming coal solution. Position L is an area of
intermediate coke formed from pitch and Freyming coal.
Position M shows the position and transmission of a
shrinkage crack, from within the Pocahontas coke into
the intermediate coke. This would suggest that a strong
bond exists at the interface between the two cokes.
Figure 13 Optical micrograph of coke prepared from base blend
Position K, otherwise this shrinkage crack would have with 5% pitch B. Position T shows a micro-crack originating from a
divided into the interface. shrinkage crack

526 FUEL, 1981, Vol 60, June

 Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

mozaic of coke from the Pocahontas coal. Similar cracks

are seen in fine-grained mozaics of the Pocahontas coal
with the crack deviating around isochromatic units of the
mozaic rather than fracturing through them.
Figure 11, Position V, shows a crack encountering a
pore in the coke. The crack instead of stopping, as would
be expected, continues at a position opposite its entry.
This indicates that all porosity will not act as crack-
stoppers. Rather, pores may possess features which
facilitate crack propagation, e.g. cusps or deviations from
sphericity’.
It would appear that some of the cracks seen in the coke
pieces after micro-strength testing have their origin in the
action of stress upon the shrinkage cracks formed by layer
plane cleavage during the contraction stage of carboni-
zation, in the domains from Pocahontas coal. Figure 12,
Position R, shows a shrinkage crack, l-2 pm width,
following the orientation of structure around a pore in a
Figure 74 Optical micrograph of coke prepared from base blend domain of Pocahontas coal-coke. The crack extends into
with 5% pitch C. Position U shows a crack originating from a
the isotropic Freyming coke, Position S, and to the right
shrinkage crack extending along an interface
of the pore into a zig-zag shaped crack in mozaics. Figure
13 shows a microcrack, < 1 pm width, originating from a
shrinkage crack at Position T. Growth of microcracks
from the tips of the shrinkage cracks occurs as predicted
by Griffiths” for elliptically terminated cracks under
stress.
Figure 14, illustrates how crack growth from the tip of a
shrinkage crack could possibly lead to failure of the coke
under stress. Position U, shows a crack starting as a
shrinkage crack and extending along the interface of
Pocahontas coke with Freyming coke before propagating
into the isotropic Freyming coke.
Not all cracks in the cokes result from the action of
stress on the tips of shrinkage cracks. Figure 1.5, shows
crack growth in an area of supra-mozaic, i.e. an area of
mozaic where the carbon layer planes are oriented in a
similar direction giving the area an isochromatic ap-
pearance. The crack has probably formed via layer plane
cleavage, similar to shrinkage cracks, due to the similarity
of layer plane orientation in the area of supra-mozaic.
Figure 15 Optical micrograph of coke prepared from base blend Figure 16, Position W, shows crack development
with 20% pitch 6. Crack growth is seen in areas of supra-mozaic around the interface of isotropic Freyming coke and the
fine-grained mozaic of intermediate coke.

Freyming and Pocahontas coals have interacted at in-

terfaces with these pitches.

Aspects of crack origin and growth

The purpose of examining the broken pieces of coke
from the micro-strength test is to look for structures
which appear to be able to withstand breakage under the
conditions of this test, as well as to look for the presence of
cracks which have not propagated sufficiently to cause
fragmentation. Factors hindering the propagation of
cracks may be suggested.
The cracks generally propagate linearly or in shallow
curves following the easiest path. Deviation of a crack
only occurs where structural changes enforce such a
change, e.g. porosity or the presence of pathways in which
propagation can occur presumably with lower energy
consumption.
Coke from the Freyming/Pocahontas coals tends to
fragment at the interfacial position of the two cokes. Figure 16 Optical micrograph of coke prepared from base blend
Within the fragment, Figure 10, Position Y, is seen the zig- with 20% pitch 6. Position W shows a crack at interface of isotropic
zag path of a crack contained within the coarse-grained Freyming coke and fine-grained mozaics of intermediate coke

FUEL, 1981, Vol 60, June 527

Carbonization and liquid-crystal (mesophase) development (22): S. Ragan and H. Marsh

However, crack development at positions of contact Community, ECSC Research Agreement No. 7220
between anisotropic and isotropic components in the EB/8/807. S. R. acknowledges direct financial support and
coke is particularly prevalent in areas where there is no H.M. acknowledges the support to the Northern Carbon
intermediate coke. Research Laboratories. S.R. and H.M. appreciate the
Thus, it would appear that increases in strength of assistance of Marion Poad and Bridget Clow.
cokes caused by pitch additions to coal blends originate
from the formation of an intermediate coke from a
coal/pitch fluid phase. This coke enhances the bonding at
interfaces between the reacting components and is re- REFERENCES
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