Authors Accepted Manuscript

Thermal and thermomechanical characteristics of

monolithic refractory composite matrix containing
surface-modified graphite

S. Mukhopadhyay, K. Dana, S. Moitra, S.

BasuMallick, T.K. Mukhopadhyay
www.elsevier.com/locate/ceri

PII: S0272-8842(15)02453-0
DOI: http://dx.doi.org/10.1016/j.ceramint.2015.12.155
Reference: CERI11950
To appear in: Ceramics International
Received date: 1 October 2015
Revised date: 17 December 2015
Accepted date: 26 December 2015
Cite this article as: S. Mukhopadhyay, K. Dana, S. Moitra, S. BasuMallick and
T.K. Mukhopadhyay, Thermal and thermomechanical characteristics of
monolithic refractory composite matrix containing surface-modified graphite,
Ceramics International, http://dx.doi.org/10.1016/j.ceramint.2015.12.155
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal pertain.
 Thermal and thermomechanical characteristics of monolithic refractory
composite matrix containing surface-modified graphite
*
S.Mukhopadhyay1 , K. Dana2, S.Moitra1, S.BasuMallick1 and T.K.Mukhopadhyay2

1
Department of Chemical Technology, Calcutta University, 92 APC Road, Kolkata 700009,
2
CSIR-Central Glass and Ceramic Research Institute , Kolkata 700032, India

Abstract

The thermomechanical analysis (TMA) and thermal characteristics of carbon-containing

refractory castable matrix with 20.0 wt% of graphite have been compared with graphite-free
high alumina based similar castable matrix. Graphite has been added both in uncoated and
coated forms, the latter having a thin sol-gel calcium aluminate coating on as-received graphite
flakes. The influence of systematic variation of microfine constituents e.g. reactive alumina, high
alumina cement etc in the matrix has been investigated in terms of the heat flow studies
obtained by differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). The
densification behavior of graphite-free and graphite-containing castable matrices has been
critically estimated by the dimensional changes in dynamic heating regime up to 1500 oC. The
role of coated graphite on improved densification behavior of refractory was explored by
microstructure and phase assemblage studies of the respective fired castable. It was further
corroborated by the transmission electron microscope (TEM) studies of surface-modified
graphites.

Keywords :A. Sintering ; B. Electron Microscopy ; C. Thermomechanical Analysis, D.Al2O3 , Carbon .

*e-mail ( Corresponding author ) : msunanda_cct@yahoo.co.in

Tel : + 91 033 2350 8386 ; fax : + 91 033 2351 9755.

1
1. Introduction

Since 1970, carbon and graphite have been utilized in combination with suitable refractory
ceramic materials e.g. alumina, to build up a composite structure appropriate for several
sectors of iron and steel making industries. Graphite/carbon additions reduce the wear on the
structure by controlling the infiltration depth due to molten slag or metal. Apart from the
increase in corrosion and penetration resistances, thermal shock resistance of the carbon
containing refractory is also improved due to low thermal expansion and high thermal
conductivity of graphite. It further confers elasticity to the structure and help absorbing
thermomechanical stresses. As such, carbon containing alumina refractories have been
increasingly popular, especially in the functional components of continuous casting operations
for steel [1-4].The flexibility in production of monolithic refractory composite, their cheaper
installation and comparable performance to shaped refractory bricks dramatically enhanced
the market of such unshaped materials, specially refractory castables.

Although the processing, properties and performance of such high-tech and heavy-duty
refractory castables have been improved significantly, their commercial use is still impeded due
to some technical flaws. The biggest drawback of carbon containing refractory is the high
temperature of oxidizing atmosphere that converts C(s) to CO(g) and/or CO 2(g). It leads to
excessive porosity and concomitant destruction of the structure in all respect. The second
disadvantage, more pertinent to the fabrication part of monolithic refractories, lies with the
water-immiscibility of graphite. Being non-wetting to water-based slurry, it is very difficult to
disperse graphite homogeneously with the other refractory constituents to obtain a monolithic
mix. Refractory scientists attempted a number of alternative routes to bypass those pitfalls by
surface modification of graphite. Among these efforts, high speed impact treatment, extruded
and pelletized graphite incorporation, molten salt synthesized coating of TiC, chemical vapour
deposited SiC film formation and sol-gel derived coatings ( e.g. Al2O3, SiO2) on graphite are
noteworthy [5-7]. However, any affirmative and elaborate reports on performance of castables
based on these modified graphites, particularly from industrial sectors, are still awaited. A
parallel effort has also been there to develop environment-friendly low-carbon carbon-
containing refractories, reducing CO2 emission in accordance with the protocols of pollution
control agencies worldwide [8]. It simultaneously fulfills the stringent requirement of low
carbon and high quality clean steels for the consumers. As such sustaining graphite/carbon
inside the refractory matrix became the need of the day. In tune with our maiden effort,
nonetheless, we continued our investigation with surface-modified graphite prepared by binary
oxide coatings adopted via cost-competent sol-gel method [9-18]. The preliminary results based
on such surface-treated graphite in monolithic composites proved to be quite interesting. We

2
document in this paper, the interaction of the calcium-aluminate coated graphite with the
reactive matrix part of the refractory at harsher condition, to verify its full-proof commercial
reality.

Carbon containing monolithic refractory itself is a very heterogeneous system. During the
interaction of coated or uncoated graphites with the heat-treated matrix part of the refractory
composite, it is utterly important to ensure carbon retention and protection in the aggressive
oxidizing atmosphere. The concept of graphite-free and graphite-containing representative
matrices have thus been adopted in this contribution. These have been separately formulated
and cast including the reactive microfines of the composite batch. Refractory matrix contains
the finer fraction (75-100 micron) with a greater reactivity, both at green and fired conditions
for binding the aggregates in a compact monolithic mass. The natural graphite below 75 micron
has therefore been incorporated to the matrix, both in surface-modified and as-received forms.
Successive thermal shocks and a very high thermal gradient (from 25 to 1700 oC) encountered
by refractory castables necessitate a comprehensive understanding of the thermomechanical
behavior of such materials. Structural spalling associated with extensive peeling of the slag-
penetrated layer further deteriorates the service life of the composite. The function of the
matrix and its microstructure, in this regard, have always been considered to render a decisive
influence on refractory properties [19].Lack of studies addressing the correlation between the
thermal and thermomechanical properties of castables containing coated graphites, still put
some obscure points that need to be clarified to upgrade the performance of such materials.
These have not been reported before in our previous contributions [9-18].The present work
unfolds the important facet on those aspects of the graphite-containing refractory matrices.

2. Experimental

The main ingredients for the synthesis of calcium aluminate precursor sol were aluminium-sec-
butoxide, hydrated calcium nitrate, deionised water, propanol, acetyl acetone, acetic and nitric
acids[9-13]. The hydrolysis and condensation reactions of the chief precursor with water-
propanol mixture at >85OC at pH ~ 3.0 resulted in a polymeric boehmite sol. Calcium nitrate
solution was added to it with constant stirring to achieve the stable sol having (1:1) mole ratio
between CaO and Al2O3. Natural flaky graphite with 97% fixed carbon has been utilized for this
work as done before. The preparation of sol-gel coating of calcium aluminate over the graphite
flakes involved several steps, namely magnetic stirring, ultrasonication, ageing and controlled
heating up to 600oC which had already been detailed elsewhere [14-18]. The TEM study of
coated graphite had been performed in the instrument JEOL JEM 2100 HR model (with accl.
voltage 80-200KV).

3
 Only the matrix part of the castable reported in our previous work, has been intimately mixed
and cast (Table1). It included the graphite fines (below 75 micron), both in coated or uncoated
forms along with others as shown in the tables. Antioxidant aluminium powder, although
included in the original castable batch (Table 1), was excluded from the 100% matrix
formulation (Table 2). This was to avoid aluminium-water interaction and evolution of excessive
hydrogen gas which can render the matrix permeable [20]. This may spoil samples earlier
before the thermomechanical study with small bars (25 mm X 6 mm). Seven kinds of refractory
matrices had been prepared to understand the interaction of graphites with the other
microfines present in castable matrix (Table 2). The first one without graphite (code: Co ), the
second one with coated graphite (C+) and the third one with uncoated graphite ( C-). The
graphite-containing C+ and C- matrices corresponded directly to the original castable batch
(Table1), prepared by proportionately increasing the 27.5 mass% matrix constituents to the
100% basis. Similarly graphite-free Co matrix has been formulated by taking 22.5% (i.e. 27.5
5.0) matrix constituents that did not contain any graphite fines (Table2).As the focus of our
study involved alumina based graphite-containing castable, some allowance was given during
formulation of 100% matrix, especially towards the quantity of graphite and microfine reactive
alumina. As such, during formulation of (C+) and (C-), graphite and micronized alumina were
taken 20.0 and 38.0wt% instead of 18.2 and 36.4wt% respectively. The later two percentages
directly correspond to the original castable matrix (Table 1). The fine adjustment of other
matrix constituents (microsilica, refractory cement and prefired spinel fines) in C+ and C- were
done by proportionately altering these to make it 100% as shown in Table 2. Four other matrix
formulations were also prepared (Table 2), keeping the 20.0% graphite content fixed (coated or
uncoated). CACG and CAG, both contained neither microsilica nor preformed spinel, and these
were replaced by increasing reactive alumina to 65%. Similarly (CAC+) and (CAC-) contained
calcium aluminate cement as the only microfine constituent, apart from constant graphite
content (20.0%).
To have a comprehensive idea on the phase changes associated with the green ceramics during
heat treatment, the thermal analysis study of refractory matrix is always considered to be
important. The DSC and TGA analyses of the graphite containing castable matrices have
therefore been conducted to conceive a quantitative measure on enthalpy change and mass loss
as a function of temperature (or time). For this purpose, the heat flow curves of all seven
reactive matrices had been separately studied. By this way, the effect of alteration of microfines
in the composite matrix (having the same graphite content) has been separately examined. This
experiment was carried out up to 1500 oC (from room temperature) in air at a rate of 10oC/min
in an instrument NETZSCH STA449F3 (model).

The dimensional change and the rate of dimensional change of the green compacts with
progressively higher temperature under load can unveil the minute changes associated with the
expansion or contraction of samples. For this reason, the TMA test has been performed up to
4
1500 oC in air atmosphere at a heating rate of 5oC/min. Three kinds of refractory matrices,
namely Co, C+ and C- had been selected for this purpose out of seven compositions. These
three directly corresponded to the original graphite-free and graphite-containing batches
(Table 1,2). Literature confirms that refractoriness of the alumina based refractory castables
bonded with spinel and high alumina cements are always better than that of the traditional
high-alumina composites bonded only with calcium aluminate cements [21]. It was too another
reason to compare TMA properties of (C+ and C-) samples with Co, and neither the
combination of (CAG and CACG) nor (CAC+ and CAC-). Cylindrical bars (25 mm X 6 mm) of these
three types were prepared maintaining the ball in hand consistency needed for refractory
castables [13,14]. Instead of traditional horizontal dilatometer, the samples were vertically
placed under a compressive load of 100 mN in a vertical thermomechanical analyzer (Model
TMA 402 F3, Netzsch, Germany). Conventional dilatometry was avoided as the sample dilation
would have been hindered by the frictional effect of base and the restraining force [22]. As a
number of reactions take place during the oxidation of carbon-based refractories, the
dimensional changes and their effect on densification at non-isothermal condition provided a
complete understanding on the thermomechanical behaviour of the materials. Green samples,
after curing in humid condition and then in open air, were dried at 110 oC prior to the TMA test.
Finally the scanning electron microscope (SEM) study of C+ castable( Table 1) fired at 1500 oC
has been studied, supplemented with EDS ( energy dispersive spectroscopy) analyses at several
points to explain the contribution of coated graphite towards better densification of the
refractory. The x-ray diffraction (XRD) patterns of Co and C+ matrices fired at 1400 oC were
studied by PANalytical instrument (XPERT-PRO) with Ni-filtrated CuK radiation at 40 kV/30 mA
and the phase assemblage of those two have been distinguished. The bulk density (BD) and
apparent porosity (AP) of Co, C+ and C- samples heat-treated at 1400 oC had been measured to
verify the extent of sintering in them. In this regard, ASTM C 20-00 method has been followed.

3. Results and Discussion

The TEM micrographs of coated graphite (Fig.1 a, b) should be discussed first that has not been
reported in our previous papers. It is well established that thin graphite nanoplatelets can be
prepared by separating graphite layers by exfoliation with suitable reagents and simultaneous
intercalation with alkali metals [23]. Acid molecules can penetrate within the gallery regions of
graphite along with the intercalants to generate first and higher stages of intercalated,
functionalized graphene layers [24]. Such exfoliation can result in graphite nanoplatelets with
thickness varying between 2-150 nm. Pre-exfoliation of graphite sheets, particularly with acetic
acid treatment and ultrasonication had been reported to enhance the interlayer spacing above
0.34nm and form nanosheets with thickness 4.5nm [25]. This result is consistent with the TEM
(fig a) of calcium aluminate coated graphite where the thickness is 5.9 nm. We suggest that

5
partial functionalization (due to oxidation) and simultaneous exfoliation of graphite flakes by
acid treatment increased the interlayer spacing. At the same time incorporation of Ca 2+ and
Al3+ions within these layers enhanced the thickness of the nanosheets with controlled clumping
[16]. Ultrasonic irradiation also assisted in forming these nanosheets with considerably
increased dimension [26]. Fig 1 also confirms that the graphene sheets are somewhat wrinkled
and folded due to their flexibility and possess multilayer structure [27]. Some needle-like
morphology in the Fig 1binfers the occasional formation of nanocomposites of graphene oxide
and doped -Al2O3 as described elsewhere [28]. In contrast to smooth surface of as-received
graphite particles, the rougher surface and presence of nanophases in the coated graphite had
already been proved by AFM and FESEM analyses [13,18], and confirmed here by TEM study. Its
influence on the refractory matrix will be discussed later.
The cementitious matrix part of the castable without graphite has been characterized first to
distinguish the effect of graphite within the matrix in the oxidizing atmosphere (Table 2). Later
on the effect of addition and alteration of microfine constituents and the effect of uncoated
and coated graphite fines has been analyzed. During hydration of the cement-bonded
refractory matrix, some stable and metastable hydrated compounds are formed, depending on
time, temperature and (water:cement) ratio. These are AH3, CAH10, C2AH8 and C3AH6 (C= CaO,
A= Al2O3 and H=H2O). The endothermic peaks observed in the respective plot (Fig.2a) are at par
with that occurring due to dehydration of traditional hydrated refractory cement. The sudden
shrinkage due to dehydration is also reflected in the corresponding dilatometric curve shown
afterwards [29]. As the temperature rises from 25oC the structures change (200oC) and
dehydration with amorphous phase formation occurs (400 oC). The complete dehydroxylation
may continue till higher temperature and CA appears above 900 oC. Within 1000-1200 oC,
grossite (CA2) appears whereas hibonite (CA6) forms above 1400 oC. It happens due to the
reaction of reactive alumina with CA and CA2 phases. At below 1200 oC, the liquidus phase
formation associated with the eutectic point of C-A-S ternary system (S=SiO2) also takes place if
silica is present in the batch. Phase diagram suggests the existence of mullite depending on the
temperature and decrease in lime content in the matrix [30]. Literature also shows the
evolution of glassy C-M-A-S phase (M=MgO) at around 1400 oC when MgO is available in the
refractory matrix. The corresponding changes in the thermal expansion have also been well
documented in literature [19].It reported a regular expansion up to 800 oC, a moderate
expansion at 1200 oC due to CA2 formation and shrinkage thereafter at above 1300 oC due to
onset of sintering process. Finally an expansion is there too above 1500 oC due to hibonite (CA6)
formation [31]. Although preformed spinel is quasi-inert (Table 1,2), its interaction with
microsilica and reactive alumina present in matrix also assists densification and shrinkage of the
refractory material.

6
Thus when the composite matrix is completely devoid of graphite (code: CO, Table 2), the sharp
exothermic peak due to oxidation of graphite at around 900 oC is not observed for obvious
reason (Fig.2a). It rather shows a diffused and broad exotherm ranging in between 800-1200 oC
[32]. The dehydration of cementitious compounds (below 400 oC), formation of C12A7 along with
crystallization of CA and CA2 (900-1200 oC) everything goes on as usual as described before.
As the quantity of reactive alumina is quite high in the matrix, two additional effects must be
present. Firstly AH3 gel formation and its dehydration (150-500 oC) are prominent. It will also
assist the formation of CA2, C-A-S (liquid phase), corundum (-Al2O3) and CA6 with progressively
higher temperature. If the lime content is reduced and microsilica is increased, subsequent
crystallization of mullite (above 1300 oC) from C-A-S liquid is likely too [33, 34]. The possibility of
crystallization of CAS2 or C2AS phases has also been explained in those references. In contrast
when the matrix contains calcium aluminate cement (80%) and uncoated graphite (20%) [code
(CAC-) in Table 2], the sharpness of the exothermic peak centred around 900 oC has been
registered well (Fig.2b). The corresponding mass loss in TGA plot also simultaneously increases
to 24% (not shown) than observed for Co (9.0%). Both of these correspond to the additional
effect due to graphite oxidation. Literature suggests that graphite oxidation temperature
ranges between 650-1000 oC, due to loss of carbonaceous materials via several
paths[35].However the main exothermic peak tip lies approximately at around 900oC(Fig. 2b)
depending on the particle size, impurities present etc associated with natural graphite [36]. As
such a linear expansion is observed 900 oC onwards in the TMA plot (furnished later) owing to
the release of gaseous species (CO and/or CO2) and pore formation accompanied by the
corresponding volumetric changes. The change in the slope of the TMA plot, as discussed in
next paragraphs, will further illustrate this feature. Controlling the oxidation of carbon based
refractory ceramics, is accomplished by the addition of several antioxidants, e.g. Al, Si, SiC, B 4C
etc. Accordingly the oxidation pattern can be categorized into active and passive types,
depending on the interaction of incoming oxygen to the refractory surface. It may result either
decrease or increase of the mass in due course, and classified respectively as non-protective
and protective oxidation [37].Finally the combined effect of sintering due to finer phases of
cement-bonded refractories and viscous flow of CAS/CMAS phases leads to significant
shrinkage as illustrated later. Crystallization of newer phases also compensate for the volume
expansion took place earlier

The heat-flow curves of the matrices of C- and CAG, in comparison with Co also show
conspicuous changes in different temperature regions (Figs. 2 and 3). Keeping graphite content
unaltered (20%), the cement content is first reduced to 15% and the rest part was made up of
reactive alumina, microsilica and preformed spinel (altogether 65% in C- matrix) as shown in
Table 2. Here TGA loss was found to be nearly 12.0% which is practically the half of that
occurred in (CAC-).It corroborates that the matrix tends to be more compact, embedding the

7
 graphite fines in a less porous structure. In fact, microsilica and micronized alumina are known
to reduce the water intake and porosity of castables by filling up the intergranular voids and
micro pores effectively. When the preformed spinel and microsilica are totally replaced by
reactive alumina(65%), the resultant DTA plot of the composite matrix (CAG) reveals almost
similar pattern and sequence to that observed in (C-)(Fig.3 a,b). As the cement (15%) and
graphite (20%) contents in (CAG) and (C-) matrices are the same, the difference in these two is
more conspicuous only due to abundant amount of reactive alumina in the former and its
consequences explained before. In fact, although those two matrices contain same amount of
graphite to that present in (CAC-), the sharpness of exothermic peak due to graphite oxidation
is not noticed in those two. This also confirms the retardation of graphite oxidation in the
matrices containing superfines of Al2O3, MgAl2O4 and SiO2 other than calcium aluminate
cement. Due to the presence of coated graphite and partially exfoliated graphite nanoplatelets
in C+ matrix , evolution of other auxiliary phases e.g. SiCxOy [38,39]and Si2N2O [15] are also
expected, apart from Al4C3 and Al2OC [20,40].The effect of coated graphite, in place of as-
received graphite in the above stated matrices (i.e. C+, CAC+ and CACG of Table 2) is also clear
in the respective DSC-TG curves (Figs.2,3).Three extra points, in this connection, should be
elucidated while comparing the DSC plots of (i) (CAC+) with (CAC-), (ii) CAG with CACG , and
(iii)(C+) with (C-).

(i) Between (CAC+) and (CAC-), the peak position and peak area at nearby 900 oC are changed in
the former (Fig. 2b), due to the presence of calcium aluminate coating as already explained
elsewhere [15]. The peaks around 1050 and 1100 oC in (CAC+) and (CAC-) can be due to CA2/CA
and CAS2/C2AS formation. Due to crystallization of newer phases from intermediate glassy
phases, these are also observed in CAG and CACG (Fig.3a). The active or passive oxidation in the
carboncontaining composite matrices may play some role for peak shift [37].
(ii) In CAG and CACG (Fig.3a), the additional endothermic peak below 400 oC can be due to
stepwise decomposition of hydrated C3AH6. Literature confirms that the principal molecules of
water from C3AH6 are freed first to form C3AH1.5 and then the rest molecules at higher
temperature [41]. For pure conventional calcium aluminate cement, the decomposition of AH3
and C2AH8 takes place between 200-300 oC, whereas that of diaspore/boehmite between 400-
550 oC [29, 42].The TGA results (Fig.3a, inset) also confirmed that weight loss is significantly
higher in CAG due to uncoated graphite.
(iii) The sharp endothermic peak near 1250 oC in both C+ and C- compositions (Fig.3b) is indicative
of melting which can be correlated to the influence of spinel (MgAl2O4) and microsilica
incorporation into the matrix. The existence of a liquid at much higher temperature (1475 oC) in
the quaternary system CA-CA2-C2AS-MA had been reported long before by M.RamakrishnaRao
[43]. The CMAS phase is believed to influence the bond linkage between preformed spinel and
CA6 crystallites that improve the thermomechanical properties of alumina-spinel castables [44].
However, a more recent work confirms that above 1200 oC, C2AS liquid can interact with
8
 magnesium aluminate spinel to precipitate CaMg2Al16O27 crystals [45]. At further higher
temperature it decomposes to yield CA6 and tertiary spinel via a transient high alumina phase
(CaMg2Al28O46).The porosity difference between (C+) and (C-) refractory specimens also remain
prominent in presence of fused alumina aggregates when the castable body is considered as a
whole. The better slag corrosion resistance due to such porosity difference had already been
addressed in our last paper [18] and not repeated here.

All these extrapolate the possibility of better densification and improved thermomechanical
behavior of the ceramic matrix containing surface-modified graphites. As the (C+) and (C-)
compositions directly correspond to the real matrices of the respective castable (Table 1,2) , we
discuss the dilatometric behavior of these two only , compared with the Co composition. The
TMA traces of these refractory composites, i.e. dimensional change and the differential plot of
dimensional change of the green compacts of Co, C+ and C- samples with progressively
increasing temperatures have been compared in these plots (Fig.4 a,b ). Amount of shrinkage,
mode of densification as well as sintering in those matrices can be understood by these plots at
different temperature regions. The following distinct features are revealed from those plots:
i) The overall patterns of all three, in terms of both dimensional change and the rate (derivative)
of dimensional change, are almost similar up to 1100 oC. Shrinkage is most prominent in Co
within 200-800oC due to its low water content and absence of graphite (Fig.4a). In fact, the
matrix of Co is inherently denser than the other two (Table 1,2). As such the early shrinkage as
well as the densification is more pronounced in less porous Co matrix [46]. It proceeds well in
advance compared to (C+) and (C-) and is mostly complete nearby 1400 oC. Consequently, the
rate of further densification in it slows down at that temperature (Fig.4b).Although the extent
of sintering is different , the similar trend (slope) in rate curves in Co and C+ is also prominent.
The possibility of major solid state reactions in similar sequences can be the reason. It is
perturbed in C- at elevated temperatures due to early oxidation in graphite and concomitant
increase in porosity. We suggest the coarsening phenomenon in (C-), with much less shrinkage
after vapor phase material transport, suppresses the overall densification of the composite
[47].
ii) Albeit, in comparison with Co and C+, a higher rate of shrinkage in (C-) is observed within
1250-1325 oC. Due to expulsion of graphite, infiltration of C-A-S liquid inside the extremely
porous matrix of C- accounts for such early shrinkage. But for (C+), it is impeded by the calcium
aluminate thin film over graphite that helps to sustain graphite at elevated temperature [16].
This is not observed in Co due to absence of graphite. Thus the shrinkage within 1250-1325 oC is
not so extensive in Co and C+ composites (Fig. 4b). The highest rate of shrinkage at the tip of
the lowermost curvature nearby 1400 oC, is quite evident in (C+) sample. It also corroborates
our previous observation on much improved physical properties of (C+) compared to (C-) [9-14].
We suggest the viscosity factor to be important within 1325-1400oC towards such notable

9
 reduction in shrinkage rate of (C-) sample. As the viscosity of C-A-S liquid decreases with
temperature, it helps the liquid to flow away from the pores present in (C-). It must hinder the
pore closure by sintering and weaken the grain to grain bonding by solid state diffusion. It had
already been corroborated by the subsidence above 1300 oC in the respective RUL plot of (C-)
castable [15]. The less porous (C+) matrix in contrast, improves the solid to solid adherence and
the liquid is arrested in isolated pockets. Obviously the extent of sintering in (C+) at 1400 oC
supersedes the other two (Fig. 4b). The sintered BD of Co, C+ and C- matrices have been found
to be 2.30, 1.92 and 1.68 g/cc respectively whereas the AP values are 31, 39 and 52%. The
difference in water intake and presence of coated or uncoated graphite in those samples are
responsible for such difference in densification behavior. The difference in XRD patterns of Co
and C+ matrices heat-treated at 1400 oC, in this regard, should be highlighted (Fig.5). As
expected, Co matrix contains plenty of corundum, spinel, hibonite with CA/CA2 as the minor
phases. Mullite has not been generated because the quantity of cement fine was quite higher
than microsilica (Table 2). The C+ matrix in contrast, shows some additional phases apart from
those appeared in Co. The strong peak of graphite was indicative of the sustainability of the
coated graphite at high temperature. Some other phases, especially Si2N2O [PDF: 01079-1539]
and SiC [PDF: 00-039-1196]appeared too. The mechanism of formation of these phases has
already been discussed elaborately in our previous articles [15,17]. These phases with high
aspect ratio reinforce the structure, improves the oxidation resistance and mechanical
properties [2-4,48].The shrinkage rate stops thereafter above 1400oC due to crystallization of
newer phases. The expansion finally occurs owing to CA6 formation in all three samples [19,31].
iii) The evolution of partially functionalized, expanded graphite with controlled clumping by Al3+
and Ca2+ions should be touched upon in this regard. The compatibility of the Ca-doped -Al2O3
phase on graphite to the rest part of the ceramic had already been extensively studied
[16,18]and it is not proposed to deal here with it in detail. It is believed that the thin ceramic
coating on graphite also contributes to the elasticity and thermomechanical behavior of the
respective matrix in (C+) as illustrated before in the TEM images. Due to strong interfacial
interaction it enhances the intimate contact between the coated graphite with cement fines
and CaO-Al2O3-SiO2phases present in the (C+) composite. The reinforcing phases like SiC and /or
SiCxOy , with different -value from the Al2O3 matrix, can also induce thermal stresses in the
matrix grain boundaries to hinder the crack propagation. Surface-modified graphites thus assist
to arrest, bridge and deflect cracks developed in the refractory during thermal shocks and
ensures better stress transfer synergy. This in turn, helps to accommodate the thermo
mechanical stress generated during slag invasion onto the refractory at aggressive atmosphere.

In this context, it is worth discussing the SEM micrograph of (C+) castable fired at 1500 oC
(Fig.6) [14]. It clearly represents a well-densified matrix with a contiguous structure. Spinel,
corundum and hibonite crystallites are visible in a less porous matrix. The EDS data taken at

10
two points (cross-marked white and black regions respectively) correspond to the following
elemental weight percent :(C=5.27, Al= 29.72, Si= 17.68, Ca= 9.19 , O= 38.14) and (C=14.10,Mg=
2.73, Al= 17.24, Si= 18.11, Ca= 7.11 , O= 40.72).These obviously correspond to C-A-S and C-M-A-
S phases surrounding the carbon-enriched regions. The thin calcium aluminate coating prevents
the debonding of graphite from the refractory, reduces its porosity and ensures the sinterability
of the matrix. Pre-exfoliated and flexible nanosheets of graphite also reinforce the castable
matrix, improving the mechanical stiffness and withstand the load at elevated temperature.
Selective cross linking of Ca2+ and Al3+ ions with the graphite, in this case, plays a pivotal role
towards the significant enhancement of overall performance of the respective castable.

4. Conclusions
The thermal and thermomechanical properties of castable matrices have been elaborately
studied to unravel the full potential of the calcium aluminate nanocoatings on graphite. From
this laboratory scale investigation it may be inferred that the sinterability of the refractory
matrix containing coated graphite conspicuously improves compared to that containing
uncoated graphite. The Ca2+ and Al3+ ions from the sol gel coating help clumping and partial
exfoliation of graphite sheets which result in a thermomechanically sound refractory. Evolution
of carbide and nitride phases additionally influences the thermomechanical property of that
matrix. It is also evident that incorporation of preformed spinel, reactive alumina and microsilica
turns the graphite-containing cementitious matrix more compact to slow down the oxidation
and expulsion of carbon.

Acknowledgement
The authors thankfully acknowledge the help extended by the Centre for Research in
Nanoscience and Nanotechnology (CRNN), University of Calcutta for providing the TEM facility
reported in this work.

11
References

1) EMM Ewais, Carbon based refractories, Journal of the Ceramic Societyof Japan,
112 (1310) (2004) 517532.
2) V. Roungos, C.G. Aneziris, Improved thermal shock performance of Al 2O3C refractories
due to nanoscaled additives, Ceramics International,38 (2012) 919927.
3) Y. Klemm, H. Biermann, C.G. Aneziris, Microstructure and mechanical properties of fine
grained carbon-bonded Al2O3C materials, Ceramics International 39 (2013) 66956702
4) J. Werner,C. G. Aneziris, S.Dudczig, Youngs Modulus of Elasticity of Carbon-Bonded
Alumina Materialsup to 1450C, J.Am.Ceram.Soc.,96 (9) (2013) 29582965
5) K.Sankaranarayanane,K.Balamurugan, M.Rigaud, Mechanicalpropertiesupto1100oC of
Al2O3MgO-extruded graphite pellets castables reinforced with steel, Ceram. Int.,
35(2009)359362.
6) S.Zhang,W.E.Lee, Improving the water-wettability and oxidation resistance
ofgraphiteusingAl2O3/SiO2 solgel coatings, J.Eur.Ceram. Soc. 23(2003)12151221
7) X. Liu, S. Zhang, Low-temperature preparation of titanium carbide coatings on graphite
flakes from molten salts, J.Am.Ceram.Soc.,91 (2008) 667670
8) V.Stein, C.G.Aneziris, Low carbon carbon-bonded alumina refractories for functional
components in steel technology, J.Ceram. Sci.Tech., 5(2)(2014)115-124
9) SunandaMukhopadhyay et al, Spinel-coated graphite for carbon containing refractory
castables, J. Am. Ceram. Soc., 92 (8) (2009) 1895-1900

10) S. Mukhopadhyay, Improved sol-gel spinel (MgAl2O4) coatings on graphite for

application in carbon containing high alumina castables, J. Sol-Gel Sci. Technol., 56
(2010) 66-74

11) SunandaMukhopadhyay et al, Characteristics of refractory castables containing mullite

and spinel coated graphites, Mater. Manuf. Process., 27 (2012) 177-184
12) Sk. A. Ansar et al, Development of mullite and spinel coatings on graphite for improved
water-wettability and oxidation resistance, Ceram. Int., 36 (2010) 1837-1844

12
13) S. Mukhopadhyay, G. Das, I. Biswas, Nanostructured cementitious sol gel coating on
graphite for application in monolithic refractory composites, Ceram. Int., 38 (2012)
1717-1724
14) S. Mukhopadhyay, S. Dutta, Comparison of solid state and sol-gel derived calcium
aluminate coated graphite and characterization of prepared refractory composite,
Ceram. Int., 38 (2012) 4997-5006
15) S. Dutta, P.Das, A.Das and S.Mukhopadhyay, Significant improvement of refractoriness
of Al2O3C castables containing calcium aluminate nano-coatings on graphite, Ceram.
Int., 40 (2014) 4407-4414
16) S. Mukhopadhyay, Nanoscale calcium aluminate coated graphite for improved
performance of alumina based monolithic refractory composite, Mat. Res. Bull., 48
(2013) 2583-2588
17) S. Dutta et al, Physical characteristics of alumina-carbon refractory castables containing
calcium aluminate-coated graphites, Interceram-Refractories , 62 (4) (2013) 294-298
18) S.Mukhopadhyay et al, In depth studies on cementitious nanocoatings on graphite for
its contribution in corrosion resistance of alumina based refractory composite, Ceram.
Int., 41 (2015) 11999-12010
19) F.Simonin, C.Olagnon, S.Maximilien and G.Fantozzi, Thermomechanical Behavior of
High-Alumina Refractory Castables with Synthetic Spinel Additions, J. Am. Ceram. Soc.,
83 (10) 248190 (2000)
20) A. Yamaguchi, Features and future development of the carbon containing refractory,
Key Engg. Mats. (Adv. Ceramics and composites), 247 (2003), pp. 239-244, Trans.
Teach. Publication, Switzerland
21) A.H.DeAza, J. E. Iglesias, P. Pena, S. De Aza, Ternary System Al2O3MgOCaO: Part II,
Phase Relationships in the Subsystem Al2O3MgAl2O4CaAl4O7, J. Am. Ceram. Soc., 83
(4) 91927 (2000)
22) S.Sinhamahapatra et al, Dynamic thermal study to rationalise the role of titania in
reaction sintering of magnesia-alumina system, Ceram. Int., 41(1) (2015) 1073-78
23) L.M. Viculis et al, Intercalation and exfoliation routes to graphite nanoplatelets, J. Mat.
Chem., 15 (2005) 974-978

13
24) E-K Choi et al, High yield exfoliation of three-dimensional graphite into two dimensional
graphene-like sheets, Chem. Commun., 46(2010)6320-22
25) L-Y Meng and S-J Park, Preparation and characterization of reduced graphene nano
sheets via pre-exfoliation of graphite flakes, Bull. Korean. Chem. Soc., 33 (1) (2012) 209-
213
26) G. Cravotto and P. Cintas, Sonication assisted fabrication and post synthetic
modifications of graphene-like materials, Chem. Eur. J., 16 (2010) 5246-5259
27) X. Su et al,A simple method for preparing graphene nano-sheets at low temperature,
Advanced Powder Technology, 24 (2013) 317-323
28) S. Chen et al, Graphene oxideMnO2 Nanocomposites for Supercapacitors, ACS
NANO,4(5) (2010) 2822-2829
29) T.Duran et al,Interactions in Calcium Aluminate Cement (CAC)-Based
Castablescontaining MagnesiaPart II: HydrationDehydration Behavior of CAC and
their Mixtures with Dead-Burned and Reactive-Grade MgO, J. Am. Ceram. Soc.,
94(3)(2011)909-917

30) D.E.Macphee and E.E. Lachowski, Cement components and their phase relations
(Chapter 3), in: P.C.Hewlett (Ed.), 4thEdn., Leas Chemistry of Cement and Concrete,
Butterworth Heinemann, Oxford, 2001, pp. 112-114

31) Y-C Ko, J.T.Lay, Thermal Expansion Characteristics of AluminaMagnesia and Alumina
Spinel Castables in the Temperature Range 8001650C, J. Am. Ceram. Soc.,
83(11)(2000)2872-2874

32) M.M.A-Sekkina et al, Phase composition of bauxite-based refractory castables, Ceram.

Int., 37(2011)411-418

33) B.A.Vazquez, A.Caballero, P.Pena, Quaternary System Al2O3CaOMgOSiO2: I, Study

of theCrystallization Volume of Al2O3, J. Am. Ceram. Soc., 86 (12) 219599 (2003)
34) B.A.Vazquez, A.Caballero, P.Pena, Quaternary SystemAl2O3CaOMgOSiO2: II, Study of
the Crystallization Volume of MgAl2O4, J. Am. Ceram. Soc.,88 (7) 19491957 (2005)

14
35) A.K. Bhattacharya, P. Bandopadhyay, Study on the physicochemical behavior of
graphite of eastern India used for refractory manufacture. Interceram - Refract.
Manual, 1(2009) 3640
36) W.Jiang et al, Thermal analysis of the oxidation of natural graphite effect of particle
size. Thermochimica Acta. 351(2000) 8593
37) H.Zuo et al, Comparison of oxidation behaviors of novel carbon composite brick with
traditional carbon brick, Ceram. Int.,41(2015)7929-7936
38) M.Luo et al, Microstructure and mechanical properties of multi-walled carbon
nanotubes containingAl2O3C refractories with addition of polycarbosilane, Ceram.
Int.,39(2013)4831-4838
39) J. Liu, H. Yan, K. Jiang, Mechanical properties of graphene platelet-reinforced
alumina ceramic composites, Ceram. Int., 39(2013)6215-6221
40) Q.Wang et al, Strengthening mechanism of graphene oxide nanosheets for Al2O3
C refractories, Ceram. Int.,40(2014)163-172
41) N.Schmitt et al, Coupling between kinetics of dehydration, physical and
mechanical behaviour for high alumina Castable, Cement and concrete
research,30(10)(2000)1597-1607
42) H.Sarpoolaky et al, Influence of Grain Phase on Slag Corrosion of Low-Cement
Castable Refractories, J. Am. Ceram. Soc., 84(2)(2001)426-434,
43) M. Ramakrishna Rao, Liquidus Relations in the Quaternary Subsystem
CaAl2O4CaAl4O7CaAl2SiO7MgAl2O4, J. Am.Ceram. Soc., 51(1)(1968)5054

44) Y.C.Ko, C.F.Chan, Effect of spinel content on hot strength of alumina-spinel castables in
the temperature range 10001500C, J.Euro.Ceram.Soc , 19(15)(1999)2633-2699

45) E.Y.Sako et al , In-Depth Microstructural Evolution Analyses of Cement-Bonded Spinel

Refractory Castables: Novel Insights Regarding Spinel and CA6 Formation, J. Am.
Ceram. Soc., 95 (5) 17321740 (2012)

46) M.W.Barsoum, Fundamentals of Ceramics, McGraw Hill, 1997, Chapter 10, pp.337

15
 47) W.D.Kingery,H.K.Bowen and D.R.Uhlmann, Introduction to Ceramics,2ndedn,John
Wiley and Sons, 1976, Chapter 10, pp.473

48) E. Karamian, A. Monshi, Influence of additives on nano-SiC whisker formation

in alumina silicateSiCC monolithic refractories, Ceram. Int., 36(2010)811-816

Figure Captions

Fig.1 (a, b) : TEM of calcium aluminate - coated graphite

Fig. 2: (a) DSC-TG plots of the graphite-free matrix (Co) ; (b) Comparison of DSC patterns
between CAC+ and CAC-matrices .

Fig. 3: (a) Comparison of DSC patterns of CAG and CACG matrices [inset : Comparison of TGA
between CAG and CACG ]; (b) Comparison of DSC patterns of C+ and C- matrices.

Fig.4: (a) Comparison of TMA by linear shrinkage vs. temperature plots of C+,C- and Co matrices
(b) Comparison of TMA by rate of expansion vs. temperature plots of C+,C- and Co matrices

Fig.5: Comparison of XRD patterns of Co and C+ matrices heat-treated at 1400 oC.

Fig.6: SEM of C+ castable fired at 1500 oC with EDS compositions at cross-marked points [14].

Table 1: Batch composition of graphite containing high alumina based refractory castable

Table 2: Representative matrix compositions of different high alumina based refractory

composite with/without coated or uncoated graphite.

16
 (a)

(b)

Fig.1 (a, b) : TEM of calcium aluminate - coated graphite

17
 (a)

(b)

Fig. 2 : (a) DSC-TG plots of the graphite-free matrix (Co) ; (b) Comparison of DSC patterns
between CAC+ and CAC- matrices

18
 (a)

(b)

Fig. 3 : (a) Comparison of DSC patterns of CAG and CACG matrices [ inset : Comparison of TGA
between CAG and CACG ]; (b) Comparison of DSC patterns of C+ and C- matrices.

19
 (a)

(b)

Fig.4: (a) Comparison of TMA by linear shrinkage vs. temperature plots of C+, C- and Co
matrices; (b) Comparison of TMA by rate of expansion vs. temperature plots of C+, C- and Co
matrices

20
Fig. 5 : Comparison of XRD patterns of Co and C+ matrices heat-treated at 1400 oC.

21


Fig.6: SEM of C+ castable fired at 1500 oC with EDS compositions at cross-marked points [14].

Table 1: Batch composition of graphite containing high alumina based refractory castable

22
Constituents Quantity
(wt%)
Aggregate : White fused alumina 72.0
(-6+16, -16+30, -30+60, -60+100, -100 mesh BS)

Matrix (below 75 m)
Micronised alumina (Al2O3 = 99.3%) 10
High alumina cement (Al2O3 = 72% , CaO = 27%) 4.0
Flaky graphite (coated or uncoated) 5.0
Preformed spinel (Al2O3 =78%) 8.0
Microsilica (SiO2=98%) 0.5

Antioxidant 0.5 27.5

TOTAL 100

Table 2 : Representative matrix compositions of different high alumina based refractory

composite with/without coated or uncoated graphite

Castable Constituents Micronised Microsilica Preformed High Uncoated Coated

Matrix alumina spinel alumina graphite graphite
(Code) cement ( Gr-2) (CA-C)

C0 45.0 2.5 34.5 18.0 0.0 0.0

C+ 38.0 2.0 25.0 15.0 0.0 20

C- 38.0 2.0 25.0 15.0 20.0 0.0

CACG 65.0 0.0 0.0 15.0 0.0 20.0

CAG 65.0 0.0 0.0 15.0 20.0 0.0

CAC+ 0.0 0.0 0.0 80.0 0.0 20.0

CAC- 0.0 0.0 0.0 80.0 20.0 0.0

23