2016

Expanded graphite and MgO-C

refractories
Advanced research
This book attempts to encompass “all things magnesia carbon refractories.” Although the magnesia industry is similar in many
respects to the much larger lime industry, there is to my knowledge no text concentrating solely on magnesia. There are,
however, several excellent texts covering the lime industry. Unfortunately, in these books magnesia is practically a footnote.
This book also contain the chemistry of graphite , graphite oxide ,expanded graphite and exfoliated graphite
This book was written to serve first as an advanced textbook for advanced undergraduate and graduate courses in MgO-C
refractories and second as a resource and reference for chemists and other scientists working in the field.

Mo’men Hassan Khalil

Egyptian Iron and Steel Company
2/1/2016
Chapter 1 Introduction Chapter 4 Experimental Work
Acknowledgment Raw materials
Preface Fabrication of MgO-C bricks
forward Batch preparation
Introduction Mixing
MgO-C Refractories Aging
Pressing
Expanded Graphite
tempering
Applications of MgO-C Refractories Characterization and measurement techniques
Electric arc furnace Phase analysis
Basic Oxygen furnace TGA analysis
Secondary refining furnace CHN analysis
Ladle Apparent porosity and bulk density
Cold crushing strength
Chapter 2 Historical review Hot modulus of rupture
History Modulus of elasticity
Oxidation resistance
Recent advances
Thermal shock resistance
Raw materials for MgO-C Refractory Notes
Magnesia
Chapter 5 Results and discussion
Graphite Structure and chemistry of graphite and expanded graphite
Resins Physical and mechanical properties
Anti-Oxidants Physical properties
Surface modification
Addition of alumina and titania AP%, B. D and CCS (before coking)
AP%, B. D and CCS (After coking)
Notes Mechanical properties
Chapter 3 Exfoliation of graphite Modulus of elasticity
Abstract Hot modulus of rupture
Introduction Thermal shock resistance
Mechanical exfoliation Oxidation resistance
Thermal exfoliation Notes
Other methods Chapter 6 Summary and conclusion
Scope of the future work
Notes
Notes
 Acknowledgment
 The information in this book is collected and introduced to you by/ chemist. Mo’men Hassan Khalil .Steel refractory chemist
supervisor at Egyptian iron and steel company Cairo – Egypt.

 Responsibilities :-
I. Supervising on different construction of lining of ladles, tundishes and continuous casting units.
II. Supervising of both mechanical and operational preparation of ladles and tundishes.
III. Sharing in selection of different refractories suitable according to the different operational variables during the
shift.
IV. Contacting with other departments engineers and technicians who are responsible in different production
processes or utilities.
V. Monitoring the operational processes of tundishes and steel ladles.

 This book contains the chemistry of graphite , graphite oxide ,expanded graphite and exfoliated graphite
 This book was written to serve first as an advanced textbook for advanced undergraduate and graduate courses in MgO-C
refractories and second as a resource and reference for chemists and other scientists working in the field.
 Last but not least, my sincere thanks to all my family members and friends who have patiently extended all sorts of help for
accomplishing this undertaking.
 Preface
 This book attempts to encompass “all things magnesia
carbon refractories.” Although the magnesia industry is
similar in many respects to the much larger lime industry,
there is to my knowledge no text concentrating solely on
magnesia. There are, however, several excellent texts
covering the lime industry. Unfortunately, in these books
magnesia is practically a footnote.

 This book also contain the chemistry of graphite , graphite

oxide ,expanded graphite and exfoliated graphite
 It may contain the methods of manufacturing the magnesia
Chapter (1) carbon bricks and the most applicable formulations of
MgO-C bricks with natural graphite and graphene sheets.
introduction Forward
 This book was written to serve first as an advanced
textbook for advanced undergraduate and graduate
courses in MgO-C refractories and second as a resource
and reference for chemists and other scientists working in
the field. Therefore, the reader will find that the chapters
are written as a teacher might teach the subject and not
simply as a reference work. Therefore, I hope that this book
will adopted for teaching numerous advanced courses in
nanotechnology application in ceramics and refractories,
material chemistry and related subjects.

 The coverage of this volume is as follows; first a detailed

introduction of Magnesia and graphite and a brief historical
account is given. This is followed by more detailed chapters
about manufacturing and testing
Introduction:
 A refractory is defined by ASTM C71 as “nonmetallic
materials having those chemical and physical properties
that make them applicable for structures or as components
of systems that are exposed to environments above 1000°F
(538°C)”. Refractories have good mechanical properties at
high temperature as well as at low temperature. They have
good corrosion and erosion resistance to molten slag,
metals and hot gases. Due to good thermo-mechanical and
thermo-chemical properties refractory materials are used
in various high temperature processes like iron and steel
making, non-ferrous metal processing, cement, glass,
chemical industries etc.
 They are normally used in high temperature furnaces, kilns,
boilers, incinerators etc. Many scientific and technological
inventions and developments would not have been
possible without refractory materials. Without the use of
refractory manufacturing of any metal is almost impossible.
Iron and steel industries are the main consumers of
refractory. So, the refractory production has to be in sync
with the demand of iron and steel industries. Better
manufacturing and application environment is demanding
a new generation of refractory material with improved
properties, performance and life with eco-friendliness.
 Refractories can be classified into three groups based on
their raw materials
a) Acidic (zircon, fireclay and silica)
b) Basic (dolomite, magnesite, magnesia-carbon,
alumina/magnesia-carbon, chromemagnesite and
magnesite-chrome)
c) Neutral (alumina, chromites, silicon carbide, carbon and
mullite)
 Refractories can also be classified into two groups based on
the manufacturing process
a) Shaped refractories (available in the form of different
brick shapes and includes the oxide and non-oxide
systems)
b) Unshaped refractories (plastic masses, ramming
masses, castables, gunning masses, mortars etc)
 Iron and steel industries are the major consumer of
refractories. India has emerged as the fourth largest steel
producing nation in the world, as per the recent figures
release by the World
Steel Association in April 2011. Total crude steel production in
India for 2010-11 was around 69 Million tons and it’s expected
that the crude steel production in capacity in the country will
increase to nearly 110 million tons by 2012-13. Further, if the
proposed expansion plans are implemented as per schedule,
India may become the second largest crude steel producer in
the world by 2015-16. As production of crude steel is
increasing at a significant speed, the production of the
refractory has also increased over the years to meet the
growing demand. Besides, there has been a phenomenal
change in refractory technology to fulfill the demand of high
quality steel production. In this context, carbon containing
refractories has found the widest applicability in BOF and EAF
furnaces and also in ladle metallurgy due to their good thermal
Shock resistance and excellent slag-corrosion resistance.
 MgO-C bricks have dominated the slag line of ladles for at
least a decade as they possess Superior slag penetration
resistance and excellent thermal shock resistance at elevated
Temperature because of the non- wetting properties of
carbon (graphite) with slag, high thermal conductivity, low
thermal expansion and high toughness. Increased steel
production has lead both refractory manufacturers and users
to resume interest on further improvement of thermo -
chemical properties of MgO-C refractories.
MgO-C Refractory:
 MgO-C brick is a composite material based on MgO and C
and bonded with high carbon containing pitch and resin, with
some metallic powder as anti-oxidants to protect the carbon.
MgO-C bricks are made by high pressure. These bricks show
excellent resistance to thermal shock and slag corrosion at
elevated temperatures. MgO-C bricks are used extensively in
 Antioxidants prevent oxidation of carbon and improve high
steel making processes especially in basic oxygen furnaces,
electric arc furnaces, lining of steel ladles, etc.
 MgO-C bricks have the following features:
a) MgO-C refractories have high refractoriness as no low
melting phase occurs between MgO and C.
b) Graphite, the carbon source, has very low thermal
expansion; hence in the
c) Composite of MgO-C the thermal expansion is low.
d) Graphite has very high thermal conductivity, which
imparts high thermal Conductivity in the MgO-C
composite, Thermal shock resistance of MgO-C is very
high because the thermal expansion is low and the
thermal conductivity is high.
e) MgO-C bricks prevent the penetration of slag and molten
steel because of the non-wettability of carbon.
f) Better ability to absorb stress, thus keeping down the
amount of discontinuous wear due to cracks.
 MgO-C bricks consist of magnesia, graphite, antioxidant and
binder. Magnesia grains are the main constituent of the
system which gives very high resistance to basic slag
corrosion, but suffer from poor thermal shock resistance.
Graphite has non-wetting nature which improves the
corrosion and thermal shock resistance of the MgO-C system
but it is susceptible to oxidation.
temperature strength by the formation of carbides. Binder
keeps the different components of the refractory together.
Volatile materials from the binder are the first to go out
leaving behind carbon.
 MgO-C refractories have found the widest applicability in
BOF and EAF furnaces and also in steel ladle due to their
good thermal shock resistance and excellent slag corrosion
resistance at elevated temperature. These properties come
due to the non-wetting nature (graphite) with slag, high
thermal conductivity and low thermal expansion of carbon.
The penetration and corrosion resistance are improved by
the formation of a nascent dense layer of MgO on the
working surface of MgO-C brick, due to oxidation of Mg
(produced in the reaction between MgO and C). But carbon
suffers from poor oxidation resistance and may oxidize to
form CO and CO2 resulting in a porous structure with poor
strength and corrosion resistance.
 Prevention of carbon oxidation is done by using antioxidants,
which reacts with incoming oxygen, gets oxidized and
protects carbon, thus retaining the brick structure and
properties. In presence of high carbon content, conductivity
of MgO-C brick increases and results in loss of heat energy
through the furnace wall. Presence of large quantities of
carbon in MgO-C brick makes the reduction of carbon
content in steel difficult. Finally the main problem for
nowadays is environmental pollution because the higher
amount of carbon produces the higher amount of CO and
CO2 which is released into the atmosphere. So the global aim
is to reduce carbon content in MgO-C refractories while
retaining the thermo-mechanical properties.
 In recent times, several attempts have been made to reduce
the carbon content. It has been reported that the presence of
nano size particles in MgO-C refractories have improved
thermal shock resistance, oxidation resistance and corrosion
resistance. In particular, the presence of nano carbon even at
low percentages has shown significant improvement of
several properties of MgO-C brick. Carbon nanofibers (CNFs)
or carbon nanotubes (CNTs) have also been investigated for
their use as carbon sources for low carbon refractories due to
their unique thermal, mechanical and chemical properties.
Recently, another new type of nanosized carbon, graphite
oxide nanosheets (GONs) was investigated for use as a
reinforced phase for the polymer matrix and ceramic matrix
composites owing to its excellent mechanical, thermal and
electrochemical properties. In this study, a different
approach has been followed to reduce the carbon content as
well as to increase the thermo-mechanical properties and
oxidation resistance. In the present work, expanded graphite
(EG) was used as a carbon source to partially replace flaky
graphite in MgO–C refractories in order to study the effect of
its addition on the microstructure and mechanical and
thermo-mechanical properties.
Expanded graphite:
 Expanded graphite (EG) is a promising material, which has
been widely used as gasket, thermal insulator, fire-resistant
composite, etc. Expanded graphite has very high surface
area. Generally EG is prepared by rapid heating of graphite
intercalation compound (GIC) which results in the abrupt
ejection or decomposition of guest molecules and the
subsequent huge unidirectional expansion of the initial
platelets. Some alternative methods have also been
proposed like coupled plasma, laser irradiation and
 microwave irradiation. Microwave irradiation among these is b) Electric Arc Furnace (EAF):
very promising, because it can be performed at room  Electric arc furnaces are used for melting steel scrap to
temperature in a short time with the consumption of lesser produce molten metal. MgO-C bricks are applied in most of
energy. the lining areas of electric arc furnaces. These bricks are
mainly used in hot spots and furnace bottoms, including the
slag line. Now a day they have also been used for bottom
blowing plugs, the sleeves of furnace-bottom tap holes and
Application of MgO-C refractory: furnace bottom electrodes of DC electric furnaces.
 Due to their good thermal shock resistance and excellent
c) Secondary refining furnace(SRF):
slag-corrosion resistance at elevated temperature MgO-C
 RH degassers are the most common among various
refractories have found the widest applicability in BOF and
secondary-refining furnaces due to their high refining
EAF furnaces and also in steel ladle. MgO-C (Magnesia
efficiency and high productivity. The use of MgO-C bricks has
carbon) refractories or Carbon containing Magnesite
been considered for reduced pressure operations. The
refractories have been extensively used by steel makers in
reaction at lower pressure at high temperatures is more
ladles that are containers for the secondary treatment of
significant. However, slag coating on bricks may eliminate the
steel.
problems at hot surface. Therefore MgO-C bricks may be
a) Basic Oxygen Furnace (BOF): usable in furnaces operating under reduced pressure.
 MgO-C refractory bricks are widely used in slag lines of BOF
d) Ladle:
(Basic Oxygen Furnace) because of their superior slag-
 A steel ladle is a container for transferring molten steel
corrosion resistance. The service life of Magnesia-Carbon
tapped from the converter or the electric arc furnaces up to
refractories used in BOFs have been pushed quite
the casting shop, reserving the steel during casting and
significantly (largely due to slag splashing and gunning
occasionally during secondary refining of the steel.
improvements) even as the service conditions have become
Refractories used for ladle lining must able to withstand the
more severe due to the increased operating temperature
increasing severity of service conditions associated with the
required for continuous casting and the need to produce
secondary steel making in order to produce various grades of
cleaner steel. These bricks have enhanced the production of
steel with stringent specifications. The condition during the
steel making by increasing the furnace availability. By using
steel refining processes is aggressive, which makes the
MgO-C bricks clean steel can be produced with less refractory
refractory materials used in steel ladles susceptible to a high
consumption.
degree of corrosion. Containing electro-fused magnesia of
 high purity, MgO-C bricks show excellent corrosion
resistance. Furthermore, special additives have been studied Notes
for the lining bricks to improve their durability.
 MgO-C refractory is one of the highest consumable refractory
items in steel sector. The demand for steel in the country is
currently growing at the rate of over 8% and it is expected
that the demand would grow over by 10% in the next five
years. So it is expected that demand of MgO-C refractories
will also increase with the demand of steel. Selection of raw
materials, their grading and grain size distribution and
composition play a very important role in the development of
various physical properties, microstructure and thermo-
mechanical properties of MgO-C refractory bricks. Various
different types of MgO (Magnesite) grains provide different
levels of corrosion resistance. Slag corrosion resistance of
MgO-C refractories can be improved by the use of fused
magnesia grains of high Bulk Density and high purity. Because
of its unique advantages and very high demand in steel
industry there is a huge scope and requirement of further
improvement in the properties of MgO-C refractories.
 History
 Carbon has been recognized as a very important component
of refractories after 1950’s.The addition of carbon results to
a better thermal and chemical resistance and hence the life
of refractory linings has been increased, which indirectly
reduces the cost of steel production.
 Nowadays carbon containing refractories have been
accepted for many different applications. MgO-C bricks are
used as an important lining material for basic oxygen
furnaces (LD converters), electric arc furnaces (EAF) and
also in ladle metallurgy for steel making and refining.
 In 1950 pitch bonded dolomite refractories and magnesia
carbon brick evolved. It was primarily developed for the

Chapter (2) basic oxygen furnace. For these refractories carbonization

was done during the preheating treatment of the ladle.
These refractories showed better thermal–spalling
resistance, inhibiting the slag penetration. In 1970 the first
HISTORICAL REVIEW 
zonal lining concept was started.
Burned and impregnated magnesia brick was developed
with fine pore size to inhibit slag penetration which
AND OBJECTIVE OF improved corrosion resistance and thermal spalling. These
refractories were applied in charge pad and other high wear

PRESENT WORK
and impact areas in basic oxygen furnaces. During this time
period for the first time the purity of magnesia became a
consideration. Thus Magnesia grain with lime to silica ratio
of 2 to 3: 1 and low boron content was used extensively to
increase the life of brick by improving the corrosion
resistance. In 1980 resin bonded magnesia-graphite brick
with higher carbon content was developed. The addition of
 antioxidants to prevent the oxidation of carbon content and
make the brick strong was started during that time period.
 After 2000 to further improve the corrosion resistance high
purity magnesia grains (fused/ sintered) having large crystal
size is being used. The type and amount of carbon content
are varied to improve the thermal conductivity and
oxidation resistance. The addition of various additives (such
as metal, alloy and inorganic compounds) was started to
achieve better hot strength, oxidation resistance and
corrosion resistance. These additives act as antioxidants and
improve the oxidation resistance. It was reported that Al in
addition to Si metal powder showed the best oxidation
resistance and high temperature strength, whereas Mg alloy
containing samples showed the maximum slag corrosion
resistance and hydration resistance properties. Oxidation
properties were studied in the presence of 2-8, 4-5, 12 and
20% ash content graphite .MgO-C containing graphite with
4-5% ash content was observed to have the best oxidation
resistance. Addition of MgAl2O4 spinel significantly improves
slag corrosion and erosion resistance of MgO–C refractory.
A study showed that 10 wt% addition of micron sized
stoichiometric spinel improves the resistance against
oxidation, thermal shock and slag penetration in MgO-C
brick particularly in the slag zone of steel ladles.
Recent advances
 A recent study of nano carbon addition in MgO-C refractory
showed that small amounts of nano carbon addition can
reduce the carbon content without affecting the other
properties.
 Nano carbon addition also increased the oxidation
resistance and the packing density as well as strength.
Another study reported an enhancement of 2.2 times in
strength for the MgO–C specimen containing 0.4 wt%
carbon nanofibers (CNFs) compared to that containing no
CNFs, owing to the crack arresting effect of CNFs. Recently,
another new study showed the effect of nanosized carbon,
graphene or graphite oxide nanosheets (GONs) which was
used as a reinforced phase for the polymer matrix and
ceramic matrix composites owing to its excellent
mechanical, thermal and electrochemical properties. In
some previous work GONs were incorporated into MgO–C
refractories as a new carbon source to improve the
mechanical and thermo-mechanical properties owing to
their morphology and high activity.
 Graphite has very high thermal conductivity. So, energy loss
is greater for MgO-C bricks. In order to reduce the energy
consumption due to loss of heat, it is preferred to have
relatively low carbon content in MgO-C refractories. But,
this leads to lower thermal shock resistance. In recent years,
the reduction of carbon content in MgO-C refractories is the
main aim of the research. Extensive research is ongoing to
reduce the carbon content of MgO-C refractories without
deterioration of its properties.
Raw materials for MgO-C
refractory:
 The raw materials play a vital role in the performance and
life of the refractories. Several research works had been
carried out to find out the effect of different raw materials
based on purity, crystallite size, porosity and other
parameters of different raw materials on the final properties
of MgO-C refractories. The main raw materials are
magnesia, graphite; antioxidants and binder like pitch
powder and resin. Details of the each of the raw materials
are described below.
I. Magnesia:
Figure. (1): Crystal structure of MgO
 Magnesia is the main constituent of MgO-C brick which
contains about 80 wt% or more of the total batch. Three
different types of magnesia raw materials are used to
produce MgO-C brick:
a) Sea water magnesia produced by firing Mg (OH) 2,
extracted from sea water.
b) Sintered magnesia produced from natural magnesite by
sintering.
c) Fused magnesia produced by melting magnesia in
electric arc furnace.
 For superior corrosion and abrasion resistance of the final
MgO-C brick the magnesia aggregate should have the
following characteristics:
a) Large periclase crystal grain to reduce the extent of the
grain boundary.
b) High ratio of CaO/SiO2 and small content of B2O3.
c) High purity and minimum impurity of magnesia.
 For the above mentioned reasons fused magnesia grains
with high purity and large grain size show better corrosion
resistance than sintered magnesia.
 II. Graphite: of graphite. Purity of graphite is also an important factor.
Impurities react with MgO and form low melting phase
which results in lower corrosion resistance and also lower
hot strength.
 Graphite’s role in MgO-C bricks can be summarized as
a) Graphite covers the spaces in between magnesia grains
and fills the porous brick structure.
b) Graphite prevents the slag penetration into the brick
due to high wetting angle between slag and graphite.
c) At higher temperature magnesia is reduced to pure
magnesium by carbon and the vaporized magnesium
comes to the surface of the brick and reoxidized to
Magnesia. Formation of this dense layer of MgO and CO
at the slag- brick interface prevents further penetration
of oxygen into the brick.
MgO + C Mg + CO
Figure (2): crystal structure of graphite
Mg + ½ O2 MgO
d) Graphite improves the thermo – mechanical properties
 Graphite is used as the carbon source because among
and spalling resistance of the brick because of its high
different commercial sources of carbon, graphite shows the
thermal conductivity and low thermal expansion. The
highest oxidation resistance. Carbon gets oxidized in
size of graphite has also a great role in improving the
oxidizing atmosphere which results a porous structure with
abrasion, corrosion and oxidation resistance of MgO-C
very poor strength. So, resistance against oxidation is very
bricks.
important for the carbon source. Due to the flaky nature of
e) Slag containing Fe2O3 has higher corrosive action than
graphite it imparts higher thermal conductivity and lower
that of containing FeO. Carbon reduces Fe2O3 to FeO
thermal expansion, resulting in very high thermal shock
and further reduction of FeO produces metallic iron,
resistance. Along with the increase of the graphite content
enriches the production of steel.
the compressibility increases during pressing and results in a
decrease in the porosity. Fine graphite particles are more
Fe2O3 + C 2FeO +CO
effective to improve the corrosion resistance of refractory.
FeO + C Fe + CO
The strength of MgO-C brick particularly during heat
treatment has also been reduced by the bigger particle size
III. Resin:
 Because of flaky and non-wetting characteristics of graphite,
it is very difficult to produce a dense brick without any
strong binder. In the early days pitch was used as binder for
MgO-C brick. But during operation pitch releases large
amounts of volatile matters, which are very toxic due to
their high content of polycrystalline aromatic compound
(PAC) like benzoalpha- pyrenes. Also to use pitch hot
pressing of the mixture was necessary. So, resin was found
to be the best binder for MgO-C refractories because of
these following properties:
a) Resin contains high amount of fixed carbon which
gives strong bonding property.
b) Resin has a high chemical affinity towards graphite
and magnesia grain.
c) Because of its thermosetting nature resin possesses
high dry strength.
d) It produces less hazardous gas than tar/ pitch.
e) At curing temperature (~ 200°C) resin polymerizes
which gives isotropic Interlocking structure.
f) Cold crushing strength (CCS) increases with the
increase of resin content.
 The desired viscosity of resin should be around 8000 cps,
which ensures proper mixing of the other raw materials.
Viscosity of resin is quite sensitive to temperature which
increases with decrease in temperature. So, in winter
viscosity of resin increases, this causes low dispersion of
ingredients in the mixer machine. Whereas in summer due
to high temperature viscosity decreases which gives less
strength in the green body and creates lamination. Powder
novalac resin is normally used to overcome this type of
difficulty. Compressibility during pressing improves with the
increase in resin content and consequently the CCS of the
tempered samples increase. The resol type resin is best as
binder among various resin types. Because of its lower
viscosity and lower content of volatile species the samples
containing resol had the lowest porosity after heating at
high temperature.
IV. Antioxidants:
 The main problems of using MgO-C bricks are the lower
oxidation resistance as well as the poor mechanical strength
of graphite which causes loosening of the constituents at
high temperature leading to reduced wear resistance as well
as resistance to chemical corrosion. The oxidations of
carbon in MgO-C refractories happen in two ways (a) direct
oxidation and (b) indirect oxidation. Direct oxidation occurs
below 1400°C and carbon is oxidized directly by atmospheric
oxygen. Indirect oxidation occurs above 1400°C and carbon
is oxidized by the oxygen from MgO or slag. The resulting
Mg vapor oxidizes again above 1500°C and generates MgO
which is called the secondary oxide phase or the dense
layer. This dense layer gives rise to resistance to further
oxidation.
2C(S) + O2 (g) 2CO
C (S) + MgO (S) Mg (g) + CO (g)
2Mg (g) + O2 (g) 2MgO (s)
 Thus to prevent oxidation of carbon, different antioxidants
such as Magnesium (Mg) , Aluminum (Al), Silicon (Si),
Boron Carbide (B4C) are used in MgO-C refractories. Due to
lower cost and higher effective protection Al and Si
antioxidants are mostly used.
 During the operation Al metal reacts with O2 and forms
alumina in the form of a fine layer. At the melting
temperature of aluminum (660oC), liquid aluminum breaks
the layer of alumina and reacts with surrounding carbon to
form aluminum carbide.
2Al (s) + 3O2 (g) → Al2O3 (s)
4Al (l) + 3C (s) → Al4C3 (s)
 At a temperature higher than 1000°C Al4C3 reacts with CO to
form Al2O3. Alumina directly reacts with surrounding
magnesia and forms MgO-Al2O3 spinel.
Al4C3 (s) + 3CO (g) → 2Al2O3 (s) + 9C (s)
MgO (s) + Al2O3 (s) → MgO-Al2O3 (s)
 B4C performs much better oxidation resistance than Al. B4C
reacts with CO to form B2O3. Then this B2O3 reacts with MgO
and produces a liquid phase compound MgO.B2O3.
B4C (s) + 6CO (g) → B2O3 (l) + 7C (s)
B2O3 (l) + 3MgO (s) → Mg3B2O6 (s)
 In this way B4C protects the carbon of MgO-C bricks and
improves the life.
 Further discussion about the methods and materials
used for the enhancement of oxidation resistance of
MgO-C refractory brick are given below.
 Improvement of oxidation resistance in graphite
for MgO−C refractory through surface
modification:
1st) Abstract
 Graphite, used as a carbon source in a conventional
magnesia−carbon MgO−C refractory, was modified with an
acid reagent, resulting in a negative charge on the surface of
graphite, to enhance the coating efficiency of aluminum Al-
phase, which was compared to the pristine graphite through
its dispersibity and oxidation behavior.
 The graphite particles with and without surface modification
were added, respectively, in an Al(NO3)3 suspension used as
a coating reagent, and then filtered at room temperature
 The modified graphite shows better dispersibity than the
pristine graphite, indicating that the coating efficiency of Al
precursor is enhanced in the modified graphite. With
respect to oxidation behavior, the modified graphite
without the coating layer is totally reacted with oxygen at
heat treatment of 900 °C in air. However, the Al-coated
graphite starts to react with oxygen at heat treatment of
900 °C and fully reacted with oxygen at heat treatment of
1000 °C, showing the gray and white colors, respectively.
 It is verified that the Al layer is individually and uniformly
formed on the surface of graphite and the oxidation
resistance of graphite is enhanced owing to the increased
coating efficiency of Al precursor.
 2nd) Introduction
 As we discuss above magnesia−carbon MgO−C refractory is
extensively used in basic furnace, electric arc furnace, and
steel ladles for its many desirable properties, such as the
corrosion resistance by less wettability with a molten metal
and the excellent thermal shock resistance by its low
thermal expansion, high thermal conductivity, and low
elasticity, due to the presence of graphite used as a carbon
source. However, the mechanical and thermal properties of
the MgO−C are continuously deteriorated owing to the
spalling phenomena and pore generation by the oxidation of
graphite. Therefore, antioxidants having a notably reactivity
with oxygen are requisitely added into the MgO−C batches
during fabrication to impede the oxidation of graphite.
Academically, almost graphite must not react with oxygen
until the oxidation of antioxidant is considerably progressed.
However, pore generation at inner site of MgO−C refractory
is unavoidable phenomenon because antioxidant can’t
effectively obstruct the oxidation of graphite in real
environments and has disadvantages, such as volume
expansion, limited content, and high cost.
 Therefore, in previous work, graphite was coated with the
coating reagent of metal precursor, especially aluminum Al -
precursor, to adequately obstruct the approach of oxygen to
graphite. In the MgO−C refractory prepared with the Al-
coated graphite, the reaction between graphite and oxygen
was interrupted by the barrier effect of Al layer formed on
the surface of graphite. In the coating process, the coating
reagent should be homogeneously coated on the surface of
graphite to get the sufficient coating effect. Four key points
should be considered for the preparation of graphite with a
high coating efficiency:
a) The coating process of a metal precursor onto graphite
is performed in an aqueous solution to increase the
dispersibility of metal precursor on the surface of
graphite
b) The surface of graphite is purified and modified with an
acid to give the hydrophilic group to the surface of
graphite.
c) The metal precursor having a high solubility with water
is used to improve the coating efficiency.
d) Metal with a high reactivity with oxygen is selected.
 In this work, to enhance the coating efficiency of Al
precursor onto graphite, the surface of graphite was
modified with an acid reagent. The coating efficiency of Al
precursor on the surface of graphites with and without
modification was investigated through its dispersibility, and
the oxidation behavior of the Al-coated graphite with
modification was discussed based on its microstructure and
phase analysis after Combustion tests.
3rd) Experimental
 The aluminum nitrate (Al (NO3)3) (3 mol/L, Sigma-Aldrich
Korea, Yongin, Korea) was used as a metal precursor. Platy
graphite, usually used in the commercial MgO−C refractory,
was suspended into the mixture of the sulfuric and nitric
acids (3:1, volume ratio) used as a modification reagent for
the surface of graphite. The mixture was sonicated for 3 h
and stirred for 24 h.
 After stirring, the acid-treated graphite was filtered and
washed with distilled water until pH=7 and then graphite
was dried at 80 °C for 48 h. The process for preparing the Al-
coated graphite is shown in fig .3

 Firstly, Al (NO3)3 was dissolved in an aqueous solution. The

graphite particles modified by the acid were mixed with the
Al (NO3)3 solutions, and then stirred at room temperature
for 1 h. The graphite coated with Al precursor was filtered,
and then dried at 80 °C for 1 h.

 The prepared powder was pre-heat treated at 300 °C for 1 h

under H2 atmosphere to increase the adhesion of Al
precursor onto the surface of graphite.

 The combustion tests for the modified graphite particles

before and after coating with Al precursor were conducted
in a range of 500−1000 °C for 1 h.

 The microstructure observation and elemental analysis for

the particles were performed using a scanning electron
microscope (SEM; Model JSM-5610; JEOL, Tokyo, Japan) Figure (3): Schematic diagram for fabricating Al-coated
and an energy dispersive X-ray spectrometer (EDS; energy graphite through acid treatment
resolution 133 eV; Oxford Inst., Oxford, UK), respectively.
The phase analysis after combustion tests was performed
using an X-ray diffractometer (Model PW 3040, Philips X-
pert MPD, Eindhoven, Netherlands).
 4th) Results and discussion
a) Dispersion of graphite and coating of Al phase
 To obstruct effectively the oxidation of graphite in the
MgO−C refractory, the Al precursor should be uniformly and
homogeneously coated on the surface of graphite and the
coating efficiency of Al precursor should be enhanced.
Therefore, the surface of graphite was modified by the acid
to provide the hydroxyl group of anion on the surface of
graphite.
 To confirm the effect of surface modification, the graphite
particles without and with modification were dispersed in
an aqueous solution, including the Al-coated graphite
particles. The stability of the graphite without and with
surface modification is shown in Fig.4.
 After acid treatment, the surface modified graphite is well
dispersed in the water without any aggregation after 3 d
(Fig. 4(b1)), probably meaning that the hydroxyl group with
a negative charge is generated on the surface of graphite by
the acid. However, the pristine graphite is precipitated
within a few minutes (Fig. 4(a1)). The pristine graphite
coated with Al precursor is more quickly precipitated than
the modified graphite coated with Al precursor in a short
period (Figs. 4(a2) and (b2)), and then the modified graphite
particles coated with Al precursor is again precipitated as
time passes (Fig. 4(b3)) owing to the disappearance of
charge by the reaction between the graphite with anion and
the Al precursor with cation. It indicates that Al precursor is
well coated on the surface of graphite. Namely, the
adhesion of Al precursor onto graphite is driven by the
attractive force between counter ions, which affect the
dispersion of hetero-phase. The mass gain for the surface
modified graphite is larger than that for the pristine graphite
in the coating of Al precursor, showing 1.5% and 1.9% (mass
fraction) based on Al element, respectively. It is confirmed
that the surface modification for graphite increases the
coating efficiency of Al precursor. Therefore, it is desirable
for following experimental to work with the surface
modified graphite.
 The results of microstructure and element analysis for the
surface modified graphite particles without and with the
coating layer are shown in Fig. 5, as a function of heat
treatment. In the graphite without the coating layer, only O
and C elements are detected (Fig. 5(a1)). In Fig. 5(b1), Al
element is evenly detected on the surface of graphite.
However, the Al layer can’t be distinctly distinguished,
because the coated Al layer is an amorphous phase after
pre-heat treatment at 300 °C.
 After heat treatment at 1000 °C, the polygonal Al2O3
particles converted from the amorphous Al layer are
completely covered on the surface of graphite, as shown in
Fig. 3(b2), assuming that the Al precursor is uniformly
coated on the surface of graphite. After heat treatment at
1000 °C, the graphite particles without and with the coating
layer show the different aspects. Various impurities are
detected for the graphite without the coating layer (Fig.
5(a2)), indicating that the graphite without the coating layer
is easily decomposed. However, in the graphite with the
coating layer, only Al, O and C elements are detected with
 increasing Al and O elements and decreasing C element
after heat treatment. Therefore, it can be inferred that the
oxidation of graphite will be suppressed by the Al layer
formed on the surface, making the oxygen barrier layer.

Figure. (4) Photographs showing dispersibility of graphite particles (Numbers 1, 2 and 3 indicate the graphite particles without
coating layer, with coating layer after 3 min and 3 d, respectively): (a1−a3) Pristine graphite; (b1−b3) Modified graphite.
 b) Oxidation behavior
 Photographs after combustion tests for the modified
graphite particles without and with the coating layer are
shown in Fig. 6. In the case of the graphite coated with Al
precursor, firstly the pre-heat treatment is progressed at
300 °C.
 As the temperature increases in combustion test, the
graphite without the coating layer is decomposed and
oxidized as shown in Fig. 6(a), showing the gray and brown
colors at 700 and 900 °C, respectively. Actually, the graphite
without the coating layer starts to react with oxygen at 700
°C, and fully reacts at 900 °C. However, when the graphite
was coated with Al precursor as shown in Fig. 6(b), the
graphite shows a sound condition in combustion test at 700
°C, and starts to react with oxygen at 900 °C.
 Finally, the Al-coated graphite, actually the coating layer,
fully reacts with oxygen at 1000 °C, showing a white color. It
means that the coating layer (Al precursor layer) has a
valuable effect as antioxidant owing to the continuous and
homogeneous coating onto the surface of graphite, delaying
the oxidation of graphite. The mass loss of the Al-coated
graphite is below 10% (mass fraction) after combustion test
at 1000 °C. Therefore, it can be said that the coating process
can enhance the oxidation resistance of graphite even
though the mass gain by the oxidation of coating layer is
considered.
c) Phase analysis
 XRD results for the modified graphites without and with the
coating layer are shown in Fig. 7, as a function of heat
temperature. The graphite peaks are detected in the
graphite without the coating layer before heat treatment,
which nearly disappears after heat treatment at 1000 °C.
However, the graphite peaks are clearly detected till heat
treatment at 900 °C for the graphite with the coating layer.
The alumina (Al2O3) and graphite peaks coexist after heat
treatment at 1000 °C, with some amorphous peaks,
indicating that the graphite is decomposed and the coating
layer is not fully crystallized.
Figure. (5) SEM morphologies and results of EDS analysis for modified graphite particles (Numbers 1 and 2 indicate before and
after heat treatments at 1000 °C for 1 h): (a1, a2) Without coating layer; (b1, b2) With coating layer.
Figure.(6) Photographs of modified graphite particles (Numbers 1 to 4 indicate the modified graphite particles after combustion
test at 500, 700, 900, and 1000 °C, respectively): (a1−a4) Without coating layer; (b1−b4) With coating layer.
Figure (7) XRD results of modified graphite particles without and with coating layer: (a) Modified graphite without coating layer
before heat treatment; (b) Modified graphite without coating layer after heat treatment at 1000 °C for 1 h; (c) Modified graphite
with coating layer after heat treatment at 500, 700 and 900 °C, respectively; (d) Modified graphite with coating layer after heat
treatment at 1000 and 1200 °C, respectively.
 Finally, the Al-coated graphite is fully transformed to Al2O3
at 1200 °C. The results are well consistent with the results of
combustion tests. As results of phase analysis, it is verified
that the oxidation resistance of graphite can be enhanced by
the coating of Al precursor.
 In this work, the methodology for increasing the coating
efficiency of Al precursor onto the surface of graphite has
been proposed. However, lots of works, such as effects of
metal precursor species and pre-heat treatment
temperature on the thermomechanical properties of the
MgO−C refractory, are still remained to optimize the coating
process of metal precursor for applying the graphite to the
MgO−C refractory, including coating morphology on the
surface of graphite with an acid treatment.
5th) Conclusions
 Graphite was modified with acid treatment to enhance the
coating efficiency of Al precursor. The surface modified
graphite shows better dispersibility than the pristine
graphite. The modified graphite particles coated with Al
precursor are precipitated as time passes, owing to the
disappearance of charge by the reaction between the
graphite with anion and the Al precursor with cation. It is
verified that Al precursor is well coated on the surface of
graphite. The evidence for coating of Al precursor can be
observed in the results of microstructure and element
analysis.
 The surface modification for graphite increases the coating
efficiency of Al precursor onto the surface of graphite,
showing mass gains of 1.5% and 1.9% (mass fraction) in the
graphite without and with surface modification,
respectively. The pristine graphite starts to reacts with
oxygen in combustion test at 700 °C, and then fully reacts at
900 °C. However, the Al-coated graphite shows a sound
condition in combustion test at 700 °C, and starts to react
with oxygen at 900 °C. The Al-coated graphite is retained in
combustion test of 1000 °C, even though the color is
changed to white.
 These results mean that the coating layer is homogeneously
and continuously coats on the surface of graphite, delaying
the oxidation of graphite. In addition, the graphite phase in
the Al-coated graphite is detected till 900 °C, and the Al2O3
and graphite peaks coexist at 1000 °C. Finally, the Al-coated
graphite is fully transformed to Al2O3 at 1200 °C.
Consequently, the Al-coated graphite with a high oxidation
resistance is successfully prepared with the surface
modification of graphite, and the Al-coated graphite
developed in this work will enhance the oxidation resistance
of MgO−C refractory.
 Improvement of oxidation resistance in graphite with an anisotropic structure and low costs. A major
for MgO−C by addition of Al and titania: drawback of this product is its content of carcinogenic
aromatics, notably benzo[a]pyrene. Coal-tar pitches contain
1st) Abstract 10,000–13,000 ppm benzo[a]pyrene.

 Hardenable artificial resins, especially Phenolic resins, are an

 The effect of TiO2- and Al-additions on the oxidation
environment-friendly alternative to benzo[a]pyrene rich
resistance and the mechanical properties of MgO–C
coaltar pitch and are the most frequently used organic
refractories is evaluated in terms of a phase evolution as a
binder in the production of magnesia–carbon bricks. They
function of the coking temperature. The formation of TiCN
can be mixed with the refractory granular materials without
and TiC crystalline phases in the bonding matrix contributes
warming. The coke residue is similar to pitch, approximately
to superior mechanical, thermal and chemical properties of
50%. A problem is the isotropic phase of the coke residue
carbon-bonded refractories.
resulting from resins leading to more oxidation, corrosion
and thermo-mechanical sensitiveness.
2nd) Introduction
 In recent years the composition of high-duty magnesia–
 On the other hand, there is a relatively new Carbo-resin
carbon bricks has been improved, especially in terms of the
product (CARBOnaceous RESin), which is a high melting
binders and additives used for better thermo-mechanical
coal-tar resin. Although it is produced out of coal it contains
properties under ecological and economical aspects. By
extremely low carcinogenic aromatics, especially the
using artificial resins – as alternative environmental friendly
benzo[a]pyrene (<300 ppm). After coking it forms, in
products against tar pitch bonded products – a higher
contrast to resins, a highly oriented graphite-like carbon
isotropic glassy phase with lower oxidation resistance and
structure.
more brittle bonding is obtained. In order to decrease this
“brittle behavior” and increase the oxidation resistance
environmental friendly artificial tar pitch binders as
 A study has been made of the reaction between MgO-C-Al
additions or as main binder parts are used.
refractories in contact with high-aluminum-content alloy
steels. They report, in the case of Al additions in MgO–C
 As we know earlier the oldest used organic binder in the
refractories, MgAl2O4 and Al4C3 phases are observed in the
production of magnesia–carbon bricks is coal-tar pitch (see
refractory bulk, and a large amount of protective MgAl2O4
first edition). Its benefits include good adhesion to the
phase is formed due to the decomposition of Al4C3 phases
granules, plastic deformability at low temperatures (low
on the refractory-metal reaction interface. Further the
softening point for improved wetting), a high yield of coke
 oxygen partial pressure is substantially reduced by the
presence of graphite in the MgO–C–Al brick during high-
temperature tests. This results in the partial nitridation of
aluminum in molten high-aluminum-content alloy steel.
White aluminum nitride (AlN) with the shape of whiskers is
formed and adheres to the surface of the MgO–C–Al brick.
Aluminum is depleted from the alloy by nitridation or the
oxidation reaction by CO gas.
 In the present work the interactions and the phase
evolution between a commercial available binder system
based on liquid phenolic resin and a powder high melting
coal-tar resin with TiO2- and Al-additions are investigated by
employing Xray diffraction (XRD), scanning electron
microscope (SEM), energy dispersive X-ray (EDX) and
electron backscatter diffraction EBSD techniques.
 In a further step, the mechanical properties and the
oxidation resistance of MgO–C refractories with TiO2- and
Al-additions are studied in terms of the cold compression
strength, the open porosity after coking and the oxidation
depth after 3 h at 1200 ◦C in air atmosphere in a special
furnace device.
3rd) Experimental
 Commercially available high quality fused magnesia with a
bulk density of 3.52 g/cm3 (Possehl, Germany) and natural
graphite flakes containing 94% carbon with a specific
surface area of 1m2/g (Graphit Kropfm¨uhl, Germany) were
used as raw materials. The liquid Novalac resin (Hexion
Specialty Chemicals, Germany) and powder CARBORES high
melting coal-tar resin (R¨utgers, Germany) were used as
binders, titania powder (Tronox, Germany) and aluminum
powder (TLS Technik, Germany) as additives. Table 1 shows
three compositions with different TiO2- and Al-additions
(the binder system, i.e. ratio of liquid Novalac resin and
powder CARBORES coal-tar resin, is identical for all three
compositions).
 In a first step, model-compositions without magnesia grains
and graphite flakes were produced. Both binders are hand-
mixed with the TiO2- and/or the Al-addition and placed in
an alumina crucible. The crucibles with the model-
compositions were filled with carbon powder in order to
inhibit the oxidation and covered with an alumina plate
before coking at temperatures between 1000 and 1500 ◦C
for 1 h. The phase evolutions of the model-compositions
were examined in air atmosphere (all compositions) and in
argon atmosphere (composition I) as a function of the
coking temperature.
 In the second step, all raw materials and additives according
to Table 1 were mixed at room temperature following the
standard commercial practice. After mixing, cylindrical
samples (50mm in diameter and 50mm in height) were
pressed (maximum pressure of 150MPa). After pressing,
the samples were cured following the standard
temperature–time curve up to 180 ◦C. The coking of the
 cylindrical samples was carried out at 1000 ◦C for 2 h in a
retort filled with carbon grit.

 The open porosity and the cold compression strength (CCS)

were determined following to EN 993, part 1 and part 5,
respectively. The oxidation tests took place in a special
electric furnace with controlled air support (10 l/min).
Samples of all compositions were placed on a rotating disc
and treated at 1200 ◦C for 3 h. The oxidation depth was
measured on the cross section at three different positions.
All experiments have been carried out with five samples
from each composition. Table 1 shows the average values
and standard deviations of open porosity, cold compression
strength and oxidation depth for all three compositions.

Composition Composition Composition Figure 8. Model-composition I, magnification 200,000×,

1 2 3 coked at 1000 ◦C in air and sealed by carbon in an alumina
crucible, whiskers based on Al4C3 and Al2OC in the previous
Open
position of aluminum grains.
porosity 13.05 ± 0.05 13.1 ± 0.05 11.3 ± 0.05
(vol %)  In the case of composition I coked at 1000 ◦C in air, Al4C3
CCS and Al2OC whiskers can be identified in the previous
22.1 ± 0.5 23.5 ± 0.5 32.2 ± 0.5
(MPa) position of aluminum grains. The Al4C3 as well as the Al2OC
Oxidation have been registered due to XRD, see also Fig. 8.
depth 9±1 3±1 2±1
(mm)
 At higher coked temperatures amorphous whiskers
containing Al, C and O due to EDX are registered. With the
aid of the EBSD, no Kikuchi line patterns can be identified
(no evidence of crystals) when the whiskers of Fig. 11 are
examined. Further according to composition I but also III at
higher coking temperatures and especially above 1300 ◦C
also Al4O4C can be additionally detected. see fig 9,10,11.

Figure 10. Model-composition I, magnification 3000×, coked

at 1200 ◦C in air and sealed by carbon in an alumina crucible,
whiskers based on Al4C3 and Al2OC and amorphous whiskers
containing Al, C, O in the previous position of aluminum
grains, at the interface carbon matrix/aluminum grain a
mostly dense AlN layer.

 Very interesting results are demonstrated in Figs. 12 and 13.

Figure 9. Model-composition I, magnification 1000×, coked
at 1200 ◦C in air and sealed by carbon in an alumina crucible,
whiskers based on Al4C3 and Al2OC and amorphous whiskers
containing Al, C, O in the previous position of aluminum
grains, at the interface carbon matrix/aluminum grain a
When model-composition I is coked at 1000 ◦C in argon and
sealed by carbon in an alumina crucible Al4C3 crystal grains
are identified and remain stable up to 1500°C.
.

mostly dense AlN layer

 Figure 11. Model-composition I, magnification 20,000×, Figure 12. Model-composition I, magnification 1000×, coked
coked at 1200 ◦C in air and sealed by carbon in an alumina at 1000 ◦C in argon and sealed by carbon in an alumina
crucible, mostly amorphous whiskers containing Al, C, O in crucible, Al4C3 crystal grains are formed
the previous position of aluminum grains.
.
 Very interesting results are demonstrated in Figs. 10 and 11.
When model-composition I is coked at 1000 ◦C in argon and
sealed by carbon in an alumina crucible Al4C3 crystal grains
are identified and remain stable up to 1500°C.
 to assume that improved properties can be achieved if
straight and dumbbell-shaped nano sized carbide whiskers
are well distributed in the matrix.Amore flexible structure
with superior thermal shock performance can be designed.

Figure 13. Model-composition I, magnification 3000×, coked

at 1000 ◦C in argon and sealed by carbon in an alumina
crucible, Al4C3 crystal grains are formed.

 The model-composition III leads at 1000 ◦C to the formation

of Al2Ti4C, a phase that is not stable at higher coking
temperatures. Very interesting is the evidence that due to
the combination of TiO2 and Al additions mostly Al4C3,
Al2OC and Al4O4C crystalline whiskers are formed, Figs. 14
and 15.
Figure 14. Model-composition III, magnification 3000×,
coked at 1500 ◦C in air and sealed by carbon in an alumina
crucible, whiskers based on Al2OC, Al4O4C and Al4C3.

 These phases remain stable and keep their crystal structure

up to higher coking temperatures (in this work up to 1500 ◦
C). Very interesting appears the shape of these whiskers;
they present a dumbbell-shaped structure. It is not difficult
 be detected and non reacted TiO2. At 1500 ◦C only TiCN can
be detected (Fig. 16).

Figure 15. Model-composition III, magnification 10,000×,

coked at 1500 ◦C in air and sealed by carbon in an alumina
crucible, whiskers based on Al2OC, Al4O4C and Al4C3.
Figure 16. Model-composition II, coked at 1500 ◦C in air and
 In a previous work the formation of dumbbell-shaped SiC sealed by carbon in an alumina crucible, TiCN grains and TiCN
whiskers in Al2O3–ZrO2–C composite refractories has been agglomerates.
studied, whereby a high amount of Si has been used. This
has to be taken under consideration because of the
interactions of steel with Si. In this work Si- and SiO2-free  The TiCN formation in composition II leads to improved
dumbbell-shaped whiskers have been developed. In oxidation resistance in comparison to composition I with the
addition composition III contains cubic TiC already from Al addition, compare Figs. 17 and 18.
1000 ◦C in air. Higher XRD peaks of TiC can be registered at
1500 ◦C. In case of the model composition II up to 1200 ◦C
no TiC or TiCN is produced. At 1300 ◦C in air cubic TiCN can
Figure 17. Oxidation tests at 1200 ◦C for 3 h in air of MgO–C samples coked at 1000 ◦C in air and sealed by carbon in an alumina
crucible, left with Al-additions, right no Al-additions.

Figure 18. Oxidation tests at 1200 ◦C for 3 h in air of MgO–C samples coked at 1000 ◦C in air and sealed by carbon in an alumina
crucible, left TiO2-additions, right TiO2/Al-additions.
 The state of the art is the addition of aluminum. This
addition leads to the formation of mostly amorphous
whiskers at elevated temperatures that inhibit the
oxidation. But the amorphous whiskers are not so sufficient
as the crystalline TiCN. Composition III exhibits a remarkable
oxidation resistance. The cubic TiC and the crystalline Al4C3,
Al2OC and Al4O4C whiskers are mainly responsible for such a
performance. In addition composition III presents
approximately 30% higher cold compression strength. It is
assumed that the dumbbell-shaped crystalline whiskers
contribute to a very tight composite bonding matrix. This
extreme tight and very hard structure can also be identified
after the oxidation tests. This correlates also with
investigations of TiC- and TiCN-coating materials as they are
applied on metallic substrates for improved abrasion
resistance of working tools. Composition II and III present a
very strong coherence between the MgO grains and the
bonding matrix also after the oxidation test. In contrast, the
structure of composition I without any Al additions is very
weak and the abrasion resistance is very low.
 It is assumed that samples coked at temperatures above
1300 ◦C would exhibit superior mechanical, thermal and
chemical properties because of a high formation of TiCN and
TiC in the compositions II and III. According to industrial
applications, composition II and especially composition III
posses superior performance to resist the hard service
conditions such as abrasion, erosion and corrosion by
metal/slag-melts as well as withstand thermal shock
attacks. With respect to their extraordinary properties by
low cost TiO2-additions the model-compositions II and III
can also be applied in the Al2O3–ZrO2–C system for the
development of submerged entry nozzles and sliding gates.
4th) Conclusion
 The addition of TiO2 and TiO2/Al in carbon bonded
refractories leads to the formation of TiCN and TiC,
respectively. These carbides improve the oxidation
resistance, the mechanical strength as well as the abrasion
resistance of the bonding matrix. In additionTiO2 in carbon-
bonded refractories with Al as an antioxidant, contributes to
the formation of mainly crystalline Al4C3, Al2OC and Al4O4C
dumbbell shaped whiskers. These whiskers present a higher
oxidation resistance in comparison to amorphous whiskers
containing Al, C and O and it is assumed that they increase
the thermal shock performance because of interlocking
mechanisms in the bonding matrix. AlN is identified only at
the interface carbon matrix/Al-grain. The whiskers in the
previous position of Al grains contain only Al, O and C.
Objective of present work
 MgO–C refractory is a crucial item for steel production
which possesses many advantages as a furnace lining. But,
there are several problems still to be resolved. Therefore
enormous scope of further research and development still
exists in this field. In recent times, the main aim of research
is to reduce carbon content in MgO-C refractories while
retaining all the good properties. A lot of attempts have
been made to reduce the carbon content while retaining the
benefits of a high carbon MgO-C refractory.
 Because of good thermal shock resistance and excellent
slag-corrosion resistance at elevated temperature MgO-C Notes
bricks have found the widest applicability in BOF and EAF
and also in steel ladle. Graphite fills the pores of MgO-C
brick and improves the non wetting property of the bricks
and thereby improves the slag corrosion resistance. But
higher amounts of graphite impose several difficulties such
as high thermal conductivity and relatively low strength
particularly at high temperatures because of high rate of
oxidation of graphite. However, the main area of concern is
the environmental pollution due to the produced CO and
CO2 during oxidation of these bricks.

 In this study, a different approach has been followed to

reduce the carbon content as well as to increase the
thermo-mechanical properties and oxidation resistance. In
this study expanded graphite has been chosen to partially
substitute the graphite phase in MgO-C refractories. Small
amounts of expanded graphite have been used to partially
replace the graphite phase in a conventional MgO-C brick
formulation and a few selected properties have been
measured. An important aspect of this work is the
fabrication of the refractory specimens in plant conditions
with characterization and property evaluation being done as
done with industrial specimens.
 Expanded graphite (EG)
 EG are normally prepared from flaky particles of acid-based
complexes passing throughout the flame of a burner. Since
the intercalate is suddenly volatilized, a huge unidirectional
expansion of the starting intercalated flakes occurs. A kind
of black snow made of pure graphite worms is recovered.
Expanded graphite (EG) has numerous actual and potential
applications, such as supports for various dispersed matters,
and for uses in gasketing, adsorption, electromagnetic
interference shielding, vibration damping, thermal
insulation, electrochemical applications and stress sensing.
Because of such a number of applications, EG is a material
of growing technological importance.

 The material has a wide range of applications, such as:

Chapter (3) a) The compression of expanded graphite particles in the

absence of a binder results in a flexible sheet material
which is useful for high-temperature gaskets.

Exfoliation of b) A refractory sealing material can be formed by adding a

binder and expanded graphite to a refractory aggregate
and heating it to yield a non-porous sealing layer.
graphite c) Expanded graphite is commercially available as a fire
extinguisher agent.
d) Expanded graphite is also commercially available as a
thermal insulator, particularly one for molten metals.
e) Expanded graphite can serve as a chemical reagent with
higher reactivity than natural graphite.

Figure19. Image of expanded graphite
Exfoliation of graphite
1st) Abstract
 The exfoliation of graphite is a phase transition involving the
vaporization of the intercalate in the graphite. Expanded
graphite (EG) is a well-known material usually produced
from various intercalation compounds submitted to a
thermal shock
. graphene with a relatively small number of defects, making
 The exfoliation of graphite is a process in which graphite
expands up to hundreds of times along the C- axis resulting
in a puffed-up material with a low density and a high
temperature resistance.
 For applications of two-dimensional graphene, commercially
viable sources are necessary. Exfoliation from bulk, stacked
graphite is the most economical way to achieve large
quantities of single layer graphene. A number of methods
have been developed to achieve exfoliation of graphite,
each with advantages and disadvantages. In this review, we
describe current exfoliation methods and techniques used
to produce single layer materials from graphite precursors.
2nd) Introduction
 Graphene, a single atomic layer of sp2-bonded carbon
atoms arranged in a honeycomb lattice, exhibits remarkable
electronic, thermal and mechanical properties. A variety of
applications have been demonstrated for graphene
materials, such as structural nanocomposites, catalyst
supports, electronic devices, and energy storage in batteries
and super capacitors.
 Several methods of preparing graphene sheets have been
developed since graphene was first isolated by Novoselov
and Geim using Scotch tape in 2004. Chemical vapour
deposition (CVD) and epitaxial growth, for instance, yield
these techniques promising for applications in electronic
devices. However, these surface-based techniques do not
scale well for applications requiring macroscopic quantities
of graphene.
 Significantly larger amounts of graphene can be produced
by physical and chemical exfoliation of bulk graphite.
 This review will discuss the bulk production of graphene via
exfoliation, focusing on the exfoliation techniques and
yields. We will first describe the exfoliation mechanisms for
different starting materials, including graphite oxide,
pristine graphite, graphite intercalation compounds, and
expanded graphite. We then describe a variety of successful
exfoliation techniques that we categorize into three major
classes: mechanical exfoliation, thermal exfoliation, and
other methods, presented in Sections, 3rd, and 4th, 5Th
respectively.
a) Mechanisms
 The stacked parallel layers in bulk graphite are separated by
3.41 A°. Although the Vander Waals attraction between the
layers is weak enough to let them slide past each other in
the direction perpendicular to the C-axis, the attraction is
strong enough to make complete exfoliation into individual
layers difficult. The first attempt by Brodie to produce
single-layer graphene sheets by exfoliation dates as far back
as 1859. Since then, many attempts have been made at
large-scale production of graphene with little success. The
isolation of graphene using the Scotch tape method
prompted new efforts to produce two-dimensional
materials by exfoliation.
 For successful exfoliation, overcoming the Vander Waals
attractions between the adjacent layers is necessary. One
method is to decrease these attractions by expanding the
distance between the adjacent layers via oxidation and
chemical intercalating reactions. This reduces these forces
significantly, as the potential energy associated with Vander
Waals forces is inversely proportional to the interatomic
separation. For example, during the oxidation of graphite,
functional groups such as hydroxyl and epoxide are inserted
and bonded to the graphitic layers. The resulting material
features disordered graphitic stacking with the d-spacing
increased from 3.4 A° to around 7.0 A°, which facilitates
exfoliation significantly.
 Another way to reduce the strength of the Vander Waals
attractions is liquid immersion. The potential energy
between adjacent layers is given by the dispersive London
interactions, which are significantly reduced with respect to
vacuum in the presence of a solvent. Coleman et al. showed
that by matching the refractive indices of the material and
the solvents, the potential may approach zero. Based on this
criterion, solvents with a surface tension of around 40 mJ
m-2 were suggested for the dispersion of carbon nanotubes
and graphene. Consequently, solvents like
dimethylformamide (DMF) and N-methyl-2- pyrrolidone
(NMP) are widely used to facilitate the exfoliation of
graphite.
 Exfoliation is often achieved by introducing additional
external forces to overcome the attractive Vander Waals
interactions between layers. The commonly used techniques
are ultrasonication and thermal treatment. During
ultrasonication, shear forces and cavitation (the growth and
collapse of micrometer-sized bubbles) act on the bulk
material and induce exfoliation. In the thermal process of
graphite oxide and graphite intercalation compounds, the
pressure due to the decomposition of the functional groups
and intercalates between layers overcomes the Vander
Waals attractions and results in exfoliation.
 The association of graphene with surfactants, polymers, and
organic can be helpful in achieving stable graphene
dispersions in solvents. Surfactants attached to the graphite
layers induce repulsive electric double layers; resulting in
stable colloidal graphene suspension; polymers and organic
molecules provide repulsive steric forces between exfoliated
sheets, preventing aggregation or reassociation. Recently,
structured solvent mixtures were also shown to prevent
restacking and allow for the formation of stable
suspensions.
b) Precursor materials
 When graphite is directly exfoliated, the resulting graphene
sheets are of high quality with good crystallinity, low defect
densities, and high conductivities. However, the yield from
pristine graphite is usually low. For example, the sonication
of graphite in organic solvents normally produces graphene
with a yield of less than wt%. Exfoliated graphene can also
be obtained from graphite intercalation compounds (GICs)
and expanded graphite (EG). GICs are graphite compounds
where atoms or molecules such as alkali metal atoms or acid
molecules are intercalated between the graphitic layers.
They thus have an increased interlayer spacing relative to
graphite, which weakens the Vander Waals interactions and
facilitates the exfoliation.
 Rapid heating of intercalated GICs produces EG, which
contains partially oxidized graphitic platelets. Compared to
direct exfoliation of graphite, EG and GICs have a better
yield of single sheets; however, graphene sheets obtained
from these precursors contain some defects.
 Graphite oxide, obtained by oxidation of graphite, has
proven to be an excellent precursor to prepare single
sheets. During oxidation, the introduction of functional
groups reduces interlayer interactions, thereby promoting
complete exfoliation of single-layer GO. While pure
graphene is highly hydrophobic, GO sheets are hydrophilic
due to oxygen functional groups on the carbon sheets. They
are therefore dispersible in a wide range of solvents, which
makes GO sheets easy to process and provides better
 surface affinity in nanocomposite applications. However, GO
sheets exhibit inferior thermal/electrical conductivity and
mechanical properties compared to pristine graphene due
to the presence of defects in the basal plane. Reduction of
GO to graphene can be carried out to restore some
conductivity, but structural weakness remains due to
permanent defects in the lattice structure.
3rd) Mechanical exfoliation
 The application of mechanical forces to solutions of layered
materials via stirring, shaking, or ultrasonication has become
one of the most important approaches to exfoliate stacked
materials. Newer techniques also utilize carefully chosen
solvents that interact favorably with the material to be
exfoliated, reducing the energy penalty of exfoliation and
reducing re-aggregation of exfoliated sheets. Intercalating
agents, surfactants, and chemical fictionalization are also
used to diminish Vander Waals interactions and keep
exfoliated products suspended in solution. The success of
these different methods is detailed below for graphite
oxide) and graphite.
a) Graphite oxide
Sonication in solvents, Graphite oxide can be exfoliated in
water by sonication due to the presence of polar functional
groups and the increased d-spacing of the material. For
many applications, however, GO sheets need to be
dispersed in organic solvents; techniques to directly
exfoliate graphite oxide in such solvents have thus been an
important area of research. Typical applications include the
GO-based polymer nanocomposites obtained via solution
processing.
 The first experimental demonstration of graphite oxide
exfoliation in organic solvents involved fictionalization of
graphite oxide with isocyanate. This reaction reduces the
amount of hydrogen bonding in the oxide layer by
converting potential hydrogen bond donors, such as
hydroxyl groups, into amides or carbamate esters. These
reactions allow for the exfoliation of graphite oxide to
monolayers at 1 mg mL concentrations in the organic
solvents dimethylformamide (DMF) and N-methyl-2-
pyrrolidone (NMP), while reducing the solubility of GO in
water. Later work demonstrated the dispersion of poly(tert-
butyl acrylate)-functionalized GO in toluene at 1 mg mL-1.
The surfactant didodecyldimethylammonium bromide
(DDAB), commonly used to disperse carbon nanotubes, has
also been used to disperse GO in chloroform at
concentrations on the order of 1 mg mL-1, showing that
even non-covalent fictionalization can be effective for this
purpose.
 Recently, however, direct exfoliation of graphite oxide in
certain organic solvents has been demonstrated without
additional fictionalization or additives, simplifying the
process. Graphite oxide has also been directly exfoliated
with moderate sonication in DMF, NMP, tetrahydrofuran
(THF), and ethylene glycol. Stable dispersions can typically
be made for concentrations on the order of 1 mg mL-1 for
organic solvents and 7 mg mL -1 for dispersions in water,
with almost all sheets existing as monolayers and diameters
on the order of 1 mm. Exfoliated graphene oxide is
electrically insulating with a measured conductivity of 0.02 S
m -1. Chemical reduction of graphene oxide with hydrazine
hydrate partially restores conductivity to a value of 2420 S
m-1.
Stirring and shaking, The strong cavitation induced by
sonication is known to help separate the layers of graphite
oxide, but it also fractures the sheets and is thus
problematic for applications requiring monolayers with
large diameters. A possible alternative to sonication is to
stir or shake graphite oxide after oxidation, which can
exfoliate the layers while maintaining their lateral size.
Stirring graphite oxide stacks with a starting lateral size of
50 mm was shown to yield GO monolayers with diameters
up to 40 mm, though no average size was reported. This is
a significant improvement over GO prepared via sonication,
which typically yields diameters in the hundreds of
nanometers and rarely exceeds a few microns. Recent work
has increased the lateral size of GO monolayers even
further by using graphite flakes with a larger initial size.
Starting with graphite flakes on the order of 300 mm, a
protocol of oxidation and shaking leads to GO sheets with
an average lateral size of 100 mm and a maximum lateral
size of 200 mm. Interestingly, this same protocol applied to
the starting material with 25 mm lateral size produced GO
sheets with lateral sizes around 15 mm.
b) Graphite
 In some ways, mechanical exfoliation of graphite is similar to
the exfoliation of graphite oxide, involving strong
mechanical forces to separate sheets from bulk material and
various strategies to keep the separated sheets suspended
rather than flocculating. However, the tighter interlayer
spacing of graphite and the lack of mutually repulsive oxide
layers makes direct exfoliation of graphite significantly more
difficult in comparison to graphite oxide; intercalating
agents were thus used to facilitate exfoliation. Furthermore,
graphene sheets are strongly hydrophobic, so that
exfoliation in polar solvents like water usually requires the
use of surfactants or other aids.
 Organic solvents assists sonication, The first successful
sonication-based exfoliation of graphite was achieved
in the organic solvent NMP. The sheets obtained were
chemically unmodified, pristine graphene; after
 A significant improvement in direct, sonication-assisted
centrifugation to remove the unexfoliated bulk
material, samples consisted of 28% graphene
monolayers and nearly 100% graphene nanosheets less
than 6 atomic layers thick. Maximum lateral sizes were
on the order of a few microns, similar to values
reported for sonicated GO. Unfortunately, solubility
was low, at 0.01 mg mL -1, and the yield was also low, at
around 1 wt%. The authors suggested that the yield
could be increased by serially re-sonicating and re-
centrifugation the unexfoliated bulk material. Due to
the relatively pristine nature of the obtained graphene,
films made from these sheets have conductivities of
approx. 6500 S m -1.
 Some improvement was achieved through the use of
different solvents, with solubilities as high as 0.03 mg mL -1
obtained with ortho-dichlorobenzene, and as high as 0.1 mg
mL-1 with perfluorinated aromatic solvents like
pentafluorobenzonitrile. The largest improvement was
made by using benzylamine and extending the sonication
time from approximately 1 hour used in previous studies to
4–6 hours, which lead to stable dispersions with
concentrations of 0.5 mg mL -1. Though these studies
showed improved stability, none of them provides a
quantitative investigation of the average lateral size or
thickness of the sheets obtained instead relying on
qualitative TEM analysis to show the presence of
monolayers and few-layer stacks.
exfoliation of pristine graphene has been achieved by using
drastically longer sonication times. A low power bath
sonicator was used to sonicate graphite powder in NMP for
up to 460 hours, yielding 4 wt% monolayer sheets and
solutions that were stable at 1.2 mg mL -1. More than 90% of
the nanosheets obtained were less than 6 layers thick, and
approximately 20% were monolayers. The average lateral
sheet size was found to decrease over time with sonication,
but asymptotically approached 1 mm. A similar procedure
was applied later, using 150 hours of bath sonication in
DMF, yielding solutions stable at 1 mg mL-1, though
unfortunately sheets obtained this way were only
characterized qualitatively by TEM to consist of a few layers,
with no quantitative analysis of lateral size or thickness.
These results demonstrate a clear advantage of long
sonication times in low power bath sonicators, although this
approach has not yet been fully explored. Extremely high
concentrations from 2 to 63 mg mL -1 of graphene
dispersions were achieved by redispersing dried exfoliated
few-layer graphene.
Surfactant assisted sonication, Exfoliating graphene in
water is particularly challenging due to the hydrophobic
nature of the sheets, but surfactants can alleviate this
problem and help exfoliated sheets to remain
suspended. Lotya et al. reported the first sonication-
based exfoliation of graphite in aqueous surfactant
solutions using the surfactant sodium dodecyl benzene
suffocate (SDBS). However, the concentration was
relatively low, typically <0.01 mg mL -1. AFM and TEM
evidence showed that the majority of sheets were less
than 6 layers thick, though less than 10% were
monolayers. Monolayer height was around 1 nm, likely
due to the persistence of surfactant molecules on the
sheets. Vacuum deposited films made from the
obtained graphene have a relatively low DC
conductivity of 35 S m -1 because of the presence of the
surfactant, which increases to 1500 S m -1 after removal
of the surfactant. In combination with low power
sonication for long times (up to 400 h), this method
was improved to produce graphene dispersions at
concentrations up to 0.3 mg mL -1.
 Since this initial work, a variety of alternative surfactants
have been used, including cationic surfactants like
cetyltrimethylammonium bromide (CTAB), natural
surfactants like sodium cholate and sodium deoxycholate
bile salts, and a bolaamphiphile. These different approaches
have typically yielded some surfactant-coated monolayer
graphene, yields as high as 10%, and typically lead to
concentrations on the order of 0.1 mg mL -1. In a rigorous
investigation, a variety of ionic and non-ionic surfactants
were explored, testing their ability to aid sonication based
exfoliation and dispersion of graphene in water. Generally,
non-ionic surfactants significantly outperformed their ionic
counterparts (Fig. 20). The best result, a dispersion of
approx. 1 mg mL -1 graphene after just two hours of
sonication, was achieved using the triblock copolymer
Pluronic P-123. Interestingly, an increase in sonication time
to 5 hours yielded solutions in P-123 at 1.5 mg mL -1,
consistent with the benefits of the extended sonication time
seen for exfoliation inorganic solvents. It has been shown
that ionic surfactants adsorb onto graphene and impart an
effective charge, providing electrostatic repulsion to prevent
graphene from aggregation. In the case of non-ionic
surfactants, which have a hydrophobic tail and a long
hydrophilic part, steric repulsions stabilize graphene.
However, additional repulsive interactions were found for
nonionic surfactants, which have been attributed to the
presence of acid groups and ether linkages interacting with
water and to the presence of a negative zeta potential value
due to adsorbed impurities.58AFM analysis revealed that
sheets obtained with the best surfactants had lateral sizes in
the hundreds of nanometers, where almost all sheets were
less than 5 layers thick, with 10–15% monolayers, their ability to produce large quantities of monolayer
consistent with other investigations of surfactant assisted
and sonication-based exfoliation.

Ionic liquid and sonication, Ionic liquids, semi-organic

salts existing as liquids below 100 °C, often have surface
energies close to that of graphene, and have emerged
as promising solvents to aid sonication-based graphite
exfoliation. The first ionic liquid used for this purpose
was 1-butyl-3-methylimidazolium bis(trifluoro-
methane-sulfonyl)imide, which led to 0.95 mg mL-1
stable dispersions of nanosheets with only one hour of
sonication. Lateral sizes of the sheets were on the order
of several microns, and the majority of sheets were less
than 5 atomic layers thick. However, no rigorous
analysis of these parameters was carried out. Recently,
a protocol of grinding graphite with mortar and pestle
Figure20 Surfactants can facilitate the exfoliation of graphite
before sonicating in 1-hexyl-3-methylimidazolium
to pristinegraphene, and can be removed from the final
hexafluorophosphate for 24 hours yielded stable material if necessary. Nonionicsurfactants have proven
dispersions at an unprecedented 5.33 mg mL -1. especially promising.
Quantitative analysis of the resulting nanosheets was
again brief, noting only the presence of some
nanosheets as wide as 4 mm, with an average thickness
of 2 nm, corresponding to 6–7 atomic layers. Given the
extremely high concentration of these suspensions,
ionic liquids will continue to be investigated for
graphite exfoliation, though questions remain about
 4th) thermal exfoliation
 Thermal exfoliation techniques are also capable of achieving
near-complete exfoliation into single-layer materials. These
approaches are in contrast to much earlier attempts at
thermally exfoliating and expanding graphite, which only
achieved partial exfoliation. Compared to mechanical
exfoliation methods, thermal exfoliation has many
advantages. First, thermal exfoliation is generally faster. For
example, using high temperature processes, exfoliation can
occur within seconds. Furthermore, most thermal
exfoliation methods produce graphene in a gaseous
environment, avoiding the use of liquids. For some
applications, such as electrodes in lithium batteries, dry
graphene is required. When graphite oxide is used as the
starting material, thermal exfoliation usually results in
simultaneous exfoliation and reduction of graphene.
 During the heating process, the functional groups attached
to the graphitic layers decompose and produce gases that
build up a pressure between adjacent graphitic layers.
Exfoliation occurs when this pressure exceeds the Vander
Waals interlayer attractions. For successful build-up of the
pressure, the starting materials are required to have
interlayer functional groups. For this reason, graphite oxide
expanded graphite, and intercalated graphite compounds
are usually used instead of pure graphite as starting
materials for thermal exfoliation.
a) thermal exfoliation of graphite oxide
High temperature thermal exfoliation, Successful
thermal exfoliation of graphite oxide to produce single
layer graphene sheets was first reported by Schniepp et
al. Dried graphite oxide was loaded into a quartz tube
and purged with argon. The quartz tube was then
quickly inserted into a furnace preheated to 1050 °C,
and within 30 seconds, exfoliation of graphite oxide
occurred. McAllister et al. later provided a detailed
analysis of the exfoliation mechanism and proposed
that thermal exfoliation only occurred when the
decomposition rate of the functional groups of graphite
oxide surpassed the diffusion rate of the evolved gases,
thus creating a high enough pressure to overcome the
Vander Waals interaction between graphene layers.
They also suggested that a critical temperature of 550
°C must be exceeded for a quick exfoliation to occur.
Following dispersion in solvents, wrinkled graphene
sheets with a minimum thickness of 1.1 nm were
revealed (Fig. 21). A statistical analysis showed that
80% of the observed flakes were single-layer sheets,
and the surface area of exfoliated graphene was
determined to be in the range 700–1500 m2 g -1 using
the Brunauer, Emmett, and Teller (BET) method with
conductivities ranging from 1 x 103 to 2.3 x 103 S m _1.
 Using the same exfoliation strategy of quick heating in a reported a surface area of 586 m2 g -1 for a mixture of
furnace preheated to 1050 °C,Wuet al. compared the graphite oxide and graphite nanosheets (GNS) that was
exfoliation results of five graphite starting materials. The irradiated with microwaves in a hydrogen atmosphere.
authors found that the smaller the lateral size and the lower
the crystallinity of the starting graphite, the better the
exfoliation. The surface areas after exfoliation ranged from
50–350 m2 g -1, suggesting incomplete exfoliation. The
graphene sheets obtained were of high quality with an
electrical conductivity approx. 105 S m -1.

 A detonation process was also reported to exfoliate graphite

oxide. A mixture of graphite oxide and picric acid, an
explosive, were sealed in a vessel. Fast decomposition of the
explosive produced a high temperature of around 900 °C
and a powerful shockwave of about 20 MPa, which
exfoliated the graphite sheets. The exfoliated graphene
sheets contained 2–5 layers with dimensions of a few
micrometers. Figure 21 thermally exfoliated graphene. (a) Tapping-mode
AFM topography image showing particles obtained by
 Other rapid heating methods to exfoliate graphite oxide, thermal exfoliation of graphite oxide. (b) An individual
including microwave irradiation and arc discharge, were also graphene sheet with a wrinkled and rough surface structure.
investigated. Using microwave heating, the exfoliation of (c) Contact-mode AFM scan of a different flake on the same
graphite oxide occurred in less than 1 min, producing sample. The cross-section through the sheet shown in (c)
exfoliated graphene with surface areas of 463 m2 g -1. These exhibits a height minimum of 1.1 nm.
microwave exfoliated graphene sheets had a conductivity of
274 S m -1. Interestingly, this microwave treated graphene
exfoliated further after chemical activation with KOH.
Specific surface area values of 3100 m2 g -1 were achieved;
the conductivity was approx. 500 S m -1. It is suspected that
this activated material is highly exfoliated and that its sheets
exhibit an extensive amount of holes and pores. Park et al.
 The GNS acted as the microwave collector and caused rapid in higher surface areas. This is in line with thermal
heating of graphite oxide. Similarly, Hu et al. demonstrated gravimetric analysis (TGA) and differential scanning
enhanced exfoliation of graphite oxide by mixing graphene calorimetry (DSC) of graphite oxide showing that
and graphite oxide precursor. They showed that the decomposition of the oxygen-containing groups in
existence of p–p conjugated regions in graphite oxide
graphite oxide occurs between 200 and 300 °C.
facilitates microwave exfoliation of graphite oxide. Wu et al.
demonstrated effective exfoliation of graphene sheets using Exfoliation was further reported in atmospheres other
hydrogen arc discharge, in which the temperature than air, for instance in argon at 275–295 °C and in
instantaneously increases to more than 2000 °C. The hydrogen at 200 °C. The latter yielded a specific surface
graphene sheets obtained exhibited an electrical area of 442 m2 g-1, close to the value reported for
conductivity of approx. 2 x 105 S m -1. After dispersion and exfoliation in air.
centrifugation, 80% of the graphene sheets were single
layers with a thickness of 0.9–1.1 nm; the monolayer yield
 Vacuum was used with the intent of further enhancing
was around 18 wt%. Two successful methods used to
exfoliation yields of graphite oxide at a temperature of 200
expedite exfoliation are insertion of intercalators and
°C. A pressure of <1 Pa surrounding the graphite oxide
mechanical grinding in ionic liquids. Acetic anhydride was
particles increased the net repulsive forces between the
used as an intercalating agent, which decomposed into
layers due to the release of functional groups. The
carbon dioxide and water vapour when subjected to high
schematics of the mechanism are shown in Fig. 22.
temperature. Graphene sheets with thicknesses of 0.7–1.3
Statistical analysis revealed that over 60% of the sheets
nm were also obtained by combining grinding and thermal
were single layers. An even lower temperature of 135 °C in a
exfoliation; yields were not reported in these studies.
vacuum oven was shown to produce graphene with a high
specific surface area of 759 m2 g -1.
low temperature thermal exfoliation, McAllister et al.
suggested a critical temperature of 550 °C for rapid
exfoliation of graphite oxide, which they observed
within seconds. Later, low temperature thermal
exfoliation was achieved by heating graphite oxide at
250 °C, 300 °C, and 400 °C in air for 5 minutes. The
exfoliated sheets had specific surface areas in the range
328– 418 m2 g -1, with the higher temperature resulting
 compounds (GICs) as starting materials. These compounds
have less functionalization than graphite oxide, which
usually features a carbon to oxygen ratio of 2 : 1, yet they
still have enough functionalization and/or expanded
interlayer distance for successful thermal exfoliation. In the
following, we review typical approaches to exfoliate these
graphitic compounds, including techniques common to both
graphite and graphite oxide.

Rapid heating methods. Li et al., Reported exfoliation

of expandable graphite by a rapid heating to 1000 °C in
forming gas (3% hydrogen in argon). Single and few-
layer graphene in ribbon and sheet form was found in
suspension after dispersion and centrifugation.
However, the yield was low; only 0.5% of the starting
material had remained in the resulting supernatant.
The authors believe that the rapid heating step, which
causes violent formation of gas from the intercalant, is
Figure 22 Schematics showing exfoliation of graphite oxide in
critical and responsible for the formation of the
high temperature under atmospheric pressure (top) and in
monolayer and few-layer graphene. The produced
low-temperature (a slow as 200° C) under high vacuum
graphene ribbons are semiconductors with band gaps
(bottom).
of varying size.

 To improve the yield, a process combining thermal

b) thermal exfoliation of graphite compounds exfoliation and intercalation of graphite was described by Li
et al. The expandable graphite was first exfoliated by rapid
 Direct thermal exfoliation of graphite typically involves heating. However, most of the exfoliated graphite was still
expanded graphite (EG) or graphite intercalation in multilayer form. The exfoliated graphite was then
intercalated with oleum (fuming sulphuric acid) and
inserted by tetrabutylammonium hydroxide (TBA) in DMF,
which further expanded the distance between adjacent
graphite layers as shown in Fig. 23a. After sonication in the
presence of a surfactant, a homogeneous suspension of
graphene with around 90% monolayers was formed.
Compared to graphene obtained from exfoliating graphite
oxide, the graphene sheets from this expandable graphite
are of high quality without significant defects (Fig. 23b and
Figure 23 (a) Schematics of graphite exfoliation after re-
c).
intercalation with sulphuric acid molecules (teal spheres) and
insertion of tetrabutylammonium hydroxide (blue spheres).
(b) and (c) Structures of graphene sheets after thermal
exfoliation of expanded graphite (b) and graphite oxide (c).

 Gu et al. described a 900 °C rapid heating exfoliation of GICs

made from natural graphite by intercalation with
concentrated sulphuric acid and hydrogen peroxide.
However, the obtained graphene sheets contained multiple
graphitic layers, thus a re-exfoliation process of graphite
was proposed. The expanded graphite obtained after
thermal expansion was re-intercalated and re-exfoliated
under the same conditions, followed by ultrasonication and
centrifugation, as shown in Fig. 24a. It was estimated that
the number fraction of single layer graphene was above 50%
with an overall yield of around 4–5 wt%. Graphene sheets
made from these methods are of high order and free of
defects, as demonstrated by Raman spectroscopy (Fig. 24b).
 Thermal expansion of GICs using an inductively coupled
thermal plasma (thermal ICP) was reported by Choi et al.
Thermal ICP was able to heat the GIC particles to >5000 K
over a millisecond time period and rapidly vaporize the
 intercalated species. Acoustic cavitation was then used to
produce graphene sheets with a low degree of defects (Fig.
25c). The conductivities ranged from 6.6 x 103 S m -1 to
8 x 103 S m -1. A survey of particles by Raman spectroscopy
revealed that 12% of the sheets were monolayers.

Figure 25 (a) and (b) SEM images of expanded graphite after

thermal ICP treatment. (c) Raman spectra of four graphene
sheets after deposition on a Si wafer.

Microwave irradiation and solvo-thermal exfoliation,

Figure 24 (a) Schematic of the re-intercalation and re-
exfoliation steps in the synthesis of graphene sheets.(b)
Raman spectra of the starting material GICs (curve a), thermal
exfoliated graphite (curve b) and graphene after dispersion
(curve c).
Microwaves were successfully used to exfoliate several
different precursors in liquid or gas environments.
Janowska et al. reported exfoliation of EG in an
aqueous ammonia solution under microwave
irradiation in the temperature range 120–200 °C. The
graphene sheets produced were less than 10 layers
thick with a yield of around 8 wt%. The authors
proposed that the excellent wetting behavior of the
ammonia solution on graphite facilitated its infiltration
of graphite, resulting in exfoliation. The spontaneous
decomposition of the ammonia solution (NH4OH) to
gaseous NH3 and H2O by microwave radiation also
contributed to the exfoliation process. Simple
microwave irradiation was also used to exfoliate EG;
 after ultrasonication in a solvent for better dispersion, prompted the intercalation of oleyl amine molecules into
graphene concentrations of 2.8–3.9 wt% were achieved expanded graphite. The high temperature and pressure
induced by solvothermal treatment may have facilitated the
exfoliation.
 Qian et al. reported solvothermal exfoliation of expanded
graphite using the highly polar solvent acetonitrile (ACN).
After centrifugation, the yield of monolayer and bilayer
graphene (thickness: 0.5–1.2 nm) was as high as 10–12
wt%.

 Direct exfoliation of pristine graphite into graphene was

demonstrated by solvothermal treatment in NMP. As shown
in Fig. 26, the obtained graphene retains its unique intrinsic
properties; no stabilizer or impurity was introduced during
the process. The authors proposed that the solvothermal
treatment increased the internal pressure and temperature,
reducing the free energy of mixing. Both the high
temperature and pressure promoted the intercalation of the
graphitic layers by solvent molecules and weakened the
layer interaction, facilitating exfoliation. However, the
report did not provide information on the yield or the
degree of the exfoliation.

 A significant variation was developed with a solvothermal

process using oleyl amine as a solvent and intercalating
reagent for exfoliation of EG. After dispersion and
centrifugation, a high yield of 60% monolayer sheets was
achieved, with surface areas of individual graphene sheets
as high as 300 mm2. The authors attributed the successful
exfoliation to the ionic interactions between oleyl amine
and the strong acids between graphitic layers, which
Figure 26 (a) Optical image showing a dark suspension of
graphene inNMP after thermal treatment. (b) TEM image of a
piece of graphene monolayer. (c) TEM image of multilayer
graphene flakes. (d) HRTEM image of a graphene monolayer
with atomic resolution.
 c) thermal exfoliation summary
 Thermal exfoliation has proven to be a very efficient method
for the preparation of graphene. Although the sheets
produced by thermal exfoliation of graphite oxide exhibit a
wrinkled and defective structure, this process allows
recovering some of the electrical conductivity lost by
oxidation. Various heating sources, temperatures and
assistive strategies have been employed, leading to great
variance in the degree of exfoliation between methods.
Both high temperature exfoliation of graphite oxide based
on rapid heating in a furnace and low temperature
exfoliation under vacuum have so far yielded the highest
surface areas of all methods. The exfoliation of expanded
graphite and graphite intercalation compounds, which
yielded high quality graphene sheets with ordered and
defect free structures, is very promising. Intercalation
techniques have been widely combined with thermal
treatments and have proven effective in increasing
exfoliation yields.
5th) Other methods
 In addition to the relatively well-developed thermal and
mechanical methods described in the sections above,
several new and promising exfoliation methods have
emerged. Although less extensively studied, these
techniques show promise.
a) Electrochemical exfoliation
 When a voltage is applied to graphite rods serving as
electrodes in a conductive solution, the rods may corrode
and yield graphene nanosheets functionalized by the
solvent. This presents a new method for exfoliating and
functionalizing graphene with different functional groups,
while potentially lessening the number of lattice defects
introduced by common oxidation methods like the
Hummers method. The first electrochemical exfoliation
functionalized graphene with ionic liquids such as methyl
imidazolium hexafluorophosphate. When a static potential
was applied, the anode corroded, yielding
imidazoliumfunctionalized flakes that were easily dispersed
in organic solvents (but not in water) via sonication. The
flakes were not analyzed before sonication, but those
obtained after sonication were 1.1 nm thick on average,
likely representing monolayers with the extra thickness
being added by functionalization. Importantly, imidazolium
functionalization is expected to reduce the electrical
conductivity of graphene less than the addition of oxide
groups. This was partially demonstrated by the improved
conductivity of polystyrene nanocomposites made with
imidazolium- functionalized graphene.
 The electrochemical method was more thoroughly
investigated by mixing different amounts of water with
water-miscible ionic liquids (Fig. 27).
 When a voltage was applied to a solution with <10% water
content, ionic liquid-functionalized graphene sheets were
generated as seen in previous work. When the voltage was
applied to a solution with >10% water content, however, a
variety of oxidized graphene products were produced,
including 8–10 nm thick nanosheets, graphene nanoribbons,
and graphene nanosheets. The researchers proposed that in
this case water was oxidized at the anode, generating
hydroxyl and oxygen radicals that attacked the edges of
individual sheets. The attached radicals opened the sheets
enough for the ionic liquid to intercalate, which depolarized
and expanded the anode to begin corrosion.
 Overall, electrochemical exfoliation represents a new and
 Thermal stress from rapid temperature changes has been
Figure 27 A voltage applied across graphite rods in a
conductive solvent can lead to exfoliation with
functionalization.
 When sulfuric acid was used as an electrolyte in place of
ionic liquids, graphene nanosheets with large lateral size,
ranging from several micrometers to tens of micrometers,
were produced. KOH was added to sulfuric acid to reduce
the acidity and minimize, though not eliminate oxidation. All
sheets were thinner than 3 nm, and more than 65% of the
sheets were thinner than 2 nm. Over 60% of the sheets
were bilayers with AB stacking, and though oxidized, they
were found to have significantly higher electron mobility
than most reduced graphene oxide. The total yield of the
graphene thin sheets was found to be 5–8 wt%.
promising method of graphite exfoliation. It can be
implemented quickly, in some cases within one hour, and
has been tuned to yield graphene sheets of different sizes
that are functionalized with different chemistries.
b) thermal quenching of graphite
proposed as another mechanism to separate layers in
graphite. The first attempt at this technique involved
quenching hot, highly oriented pyrolytic graphite (HOPG) in
an aqueous ammonium hydrogen carbonate solution. The
HOPG was bent to introduce cracks and rapidly heated to
1000 °C, then quickly quenched to room temperature in a
bath of cool water containing 1.0 wt% ammonium hydrogen
carbonate, which was found to be significantly more
effective than quenching in pure water. The process yielded
sheets with thicknesses between 0.4 and 2 nm and
 diameters in the range 1–80 mm. The total yield and the
distribution of sheet sizes were not reported. The use of
more loosely packed, expanded graphite (EG) as a starting
material improved upon the technique, leading to a 15 wt%
yield of nanosheets less than 5 layers thick after one round
of quenching and an 80 wt% yield of such sheets after 5
sequential rounds of quenching, with 10% of this product
consisting of monolayers. Lateral sizes were on the order of
5–10 mm; quenching in pure water was significantly less
effective than in ammonia or hydrazine hydrate solutions.
 Thermal stress has also been used to exfoliate synthesized
graphite products. Microwave synthesis was used to
carbonize metal phthalocyanine compounds at 450 °C,
producing synthetic stacked graphite structures. The stacks
were then exfoliated by rapid cooling to 28 °C, 4 °C, and
- 105 °C. Cooling to 28 °C and 4 °C led to end products with 8
and 4 layers of thickness, respectively; cooling to -105 °C led
to a monolayer yield as high as 60%; as many as 90% of the
particles were single or double layers of pure graphene. This
temperature dependence shows great promise for
producing large amounts of monolayer graphene.
c) super critical fluid exfoliation
 A final method of separating graphite layers is to intercalate
them with a supercritical fluid, which is expanded to push
the graphene layers apart. This technique is potentially very
fast, and has yielded pristine graphene nanosheets. The first
supercritical exfoliation of intercalated graphite using CO
yielded sheets of a few micrometers in diameter, but the
smallest sheet thickness was 3.8 nm, corresponding to
about 10 layers. Much better results were achieved in a
later study using DMF, NMP, and ethanol instead of CO in
combination with a brief initial sonication of the materials.
All three solvents led to well-dispersed solutions at 2–4 mg
mL -1, where all sheets had less than 10 layers, including 10%
monolayers. Subsequent efforts improved this method using
1-pyrene sulfonic acid sodium salt (1-PSA) surfactants
during expansion, improving the percentage of monolayers
from 10% to 60%. Given the significant number of pristine
monolayers attained and the ease of processing, these
supercritical fluid techniques are very promising.
6th) Applications
a) gaskets seal and packings
 The compression of exfoliated graphite particles in the
absence of binder results in a flexible sheet material which is
useful for high temperature gaskets . by compressing
exfoliated graphite together with a reinforcing metal layer, a
gasket capable of withstanding an internal pressure of
34.500 kNm-1 can be formed. To provide packings which
prevent the seizing of the shaft materials, one cane vapor
deposite a metal with a low melting point such as lead on
the inner surface of an exfoliated graphite and furan resins
serve as gaskets with low adhesion to pressing plates.
 A refractory sealing material can be formed by adding a
binder and exfoliated graphite to refractory aggregate and
heating to yield a non-porous sealing layer. The sealant is
 specially useful for preventing gas leakage from blast attraction, which compromises the efforts made during
furnaces and other refractory pressure vessels. exfoliation. A better understanding of colloidal suspensions
of graphene will promote the exfoliation of graphene in
 A packing material exhibiting high sealing strength under solvents and achieve suspensions with higher
repeating heating cycles is a composite of exfoliated concentrations.
graphite. Notes
b) thermal insulators
 Exfoliated graphite is commercially available as a thermal
insulator. Particularly one for molten metals. As contact
with a molten metal provides enough heat for exfoliation .
Intercalation graphite (not exfoliated) is commercially
available under the name “hot top compound” for use at
the top of molten metals where it exfoliates immediately.

7th) Conclusion

 Bulk exfoliation of graphite is of great importance, as many

applications rely on large scale production of exfoliated
materials with controlled properties. Mechanical and
thermal exfoliation of graphite oxide and graphite are
established as the two major techniques. Substantial effort
has been made to improve the yield and degree of
exfoliation, but the yield of monolayer graphene is still quite
low; in many cases centrifugation is thus used to remove
unexfoliated material. Exfoliation methods with higher
yields are still of critical interest.

 Furthermore, once graphene sheets are exfoliated in

solvents, they tend to aggregate due to Vander Waals
 Raw materials
 Commercially available high quality with low impurity fused
magnesia (FM), natural flakes graphite, aluminum metal
powder (- 150 μm), boron carbide powder and expanded
graphite were used to maintain the granulometry of the
mixture. Liquid resin and resin powder were taken as
additives of base raw materials for the fabrication of low
carbon graded MgO-C brick.

 As mentioned earlier, this research work is centered around

the preparation of expanded graphite to use in MgO-C

Chapter (4)
refractory as partial replacement of graphite.

 In this present work, high purity magnesia, FM 97 was taken

Experimental work as the raw material for fused magnesia, considering the
selection criteria like purity, CaO/SiO2 ratio, low Fe2O3
content and large crystals in the range of 500-1500 μm. High
purity graphite, 97 FC, was taken as a raw material for
carbon and resol resin (novalac type) was used as binder.
The chemical properties of magnesia, flake graphite and
liquid resin are given in the tables below.
 Table 2: chemical composition in percentage of fused magnesia
Fabrication of MgO-brick
 The expanded graphite was used to replace a part of the
Raw graphite phase for the preparation of a limited number of
MgO% Al2O3% SiO2% CaO% Fe2O3% Na2O%
material MgO-C refractory bricks.

Fused
97.10 0.07 0.40 1.40 0.50 0.50
magnesia a) Batch preparation
 Different batches of MgO-C brick were prepared by taking
the same amount of MgO, resin and anti-oxidant contents.
Table 3: chemical analysis of flaked graphite
However, Different compositions of MgO-C bricks have been
Volatile fabricated using different amounts of expanded graphite as
Raw materials Carbon % Ash %
matter% partial replacement of the natural flake graphite. All the
Flake graphite 97.05 0.69 2.26 batches were prepared under identical conditions. All the
variations done in the study are compared with the
conventionally used MgO-C brick composition prepared
under similar conditions.
table 4: physical and chemical analysis of liquid resin
Properties Liquid resin b) Mixing
Viscosity cps at 25.0°C 8500-9000  The purpose of mixing the raw materials is to make a
Specific gravity at 25.0°C 1.23 refractory batch and transform all the solid components and
Non volatile matter % 80.10 the liquid additions into a macro homogeneous mixture that
Fixed carbon % 47.85 can be subsequently molded or shaped by one of the
Moisture % ~ 4.0 numerous fabrication methods employed by modern
refractory manufacturers. All the above batches were
separately mixed in a pan mixer at room temperature for a
period of 45 minutes. All the solid raw materials and liquid
additives are mixed in a sequence to get a macro
homogeneous mixture.
 c) Aging
 After homogeneously mixing of the materials, the batches
were kept for 2 hour for ageing. During aging the
polymerization of resin takes place by developing carbon -
carbon bonds.
d) Pressing
 The mixed materials after aging were compacted to give a
desired shape by pressing. The aged mixtures were pressed
uniaxially by hydraulic press in a steel mold. An appropriate
weight of each mixture was taken to get the desired green
density and the size of the brick. The steel mold was cleaned
using cotton and brush after each pressing. To avoid
stickiness between the mixture and mold, kerosene was
used as a lubricating agent. The mixtures were charged
slowly into the mold cavity and leveled uniformly in order to
avoid lamination in the pressed bricks.
e) Tempering
 Tempering is the heat treatment process of the refractories
at low temperature to remove volatile matters from the
organic green binders and to impart enough green strength
for handling. By this process the chemical bond is developed
in the refractory grains and the bonding phase. Tempering
of the pressed green bricks was done at 200oC for 12 hours.
With the increase in temperature phenolic resin got
converted to carbonaceous phase which helped in
developing a stronger carbonaceous bond for the refractory
brick and increased the mechanical strength of the brick.
f) Coking
 After tempering the bricks were cut into different pieces
having different sizes for the purpose of different testing.
Coking was carried out at 1000oC for 4 h under reducing
atmosphere (carbon bed).
Characterization and measurement
techniques
a) Phase analysis
 Phase analysis of the samples was carried out by standard
powder x-ray diffraction technique using Cu Kα radiation
with a step-scanning speed of 227o/min. Diffraction
patterns were analyzed by X’pert HighScore software.
Intensity ratios were calculated from the digital counts for
the relevant peak positions (highest peaks of each of the
phases).
b) TGA analysis
 Thermal analysis of the samples was carried out primarily to
determine the oxidation temperature of graphite and also
to measure the amounts of residue, which has been
assumed to the quantity of silicon carbide contained in each
of the samples prepared in this investigation. For this
purpose, a small quantity of the sample was subjected to
TGA analysis in flowing air atmosphere with a heating rate
of 5oC/minute.
 c) CHN analysis
 CHN analysis measures carbon, hydrogen and nitrogen
elemental content in a wide range of sample matrices, sizes
and concentrations, with accuracy and precision. It is a
rapid, accurate, inexpensive composition and purity test.
Typically, 1.0 to 3.0 mg is enough for an analysis with a
detection limit of 0.02% when analyzing for Carbon,
Hydrogen and Nitrogen. In its simplest form, simultaneous
CHN analysis requires high temperature combustion in an
oxygen-rich environment.
d) Micro-structure of composite by SEM
 Microstructures of natural flake graphite, expanded graphite
were studied using standard Scanning Electron Microscopes
(JEOL-JSM 6480LV). The accelerating voltage was 15/20 kV.
The powders were fixed on a self-adhesive carbon tape. For
micro-structural analysis of MgO-C samples we cut thin
pieces from the bricks. Then those thin slices of samples
were polished by various grades of abrasive papers and
diamond paste.
e) Apparent porosity (AP) and bulk density (B.D)
 AP is defined as ratio of the total volume of the closed pores
to its bulk volume and expressed as a percentage of the bulk
volume. Closed porosity is the pores that are not penetrated
by the immersion liquid, whereas open porosity are those
pores which are penetrated by the immersion liquid. AP was
measured as per the standard of IS: 1528, Part-8 (1974)
both for tampered and coke samples. The Archimedean
evacuation method generally measures both bulk density
and apparent porosity.
 The test samples were cut from the tempered bricks. After
taking dry weight all the samples were put into a container
and water was added. Then the container was heated for 2
hrs. So that all the open pores are filled with water. After
that, the suspended weight (W2) and soaked weight (W3)
were taken and AP was calculated as follows:
𝐖𝟑 − 𝐖𝟏
𝑨𝑷 = ∗ 𝟏𝟎𝟎
𝐖𝟑 − 𝐖𝟐
 BD is the ratio of the mass of the dry material of a porous
body to its bulk volume expressed in gm/cm3 or kg/m3,
where bulk volume is the sum of the volumes of the solid
material, the open pores and the closed pores in a porous
body. BD was measured as per the standard of IS: 1528,
Part -12 (1974) both for tampered and coke samples.
 Whereas true density is the ratio of mass of the material of
a porous body to its true volume and true volume is the
volume of solid material in a porous body.
𝐖𝟏
𝑩. 𝑫 = ∗𝛒
𝐖𝟑 − 𝐖𝟐
WHERE, 𝛒 density of liquid at test temperature
 f) Cold crushing strength (CCS)
 Cold crushing strength of refractory bricks and shapes is the
gross compressive stress required to cause fracture. The
cold crushing strength of the tempered and coked samples
was measured as per ASTMC-133. The test samples were
cut from the standard brick samples. Cold crushing strength
of the refractories is measured by placing a suitable
refractory specimen of on flat surface followed by
application of uniform load to it through a bearing block in a
standard mechanical or hydraulic compression testing
machine. The load at which crack appears in the refractory
specimen represents the cold crushing strength of the
specimen. The load is applied uniformly on the sample in
the flat position. It is expressed as kg/cm2.
 The working formula for calculating CCS is given by,
𝐋𝐨𝐚𝐝 (𝐤𝐠)
𝑪𝑪𝑺 =
𝐀𝐫𝐞𝐚(𝐂𝒎𝟐 )
Figure 28. Schematic diagram of CCS
g) Hot modulus of rupture (HMOR)
 The modulus of rupture of refractory specimen is
determined as the amount of force applied to a rectangular
test piece of specific dimensions until failure occurs. This
test method covers the determination of the modulus of
rupture of carbon-containing refractories at elevated
temperatures in air. It was determined as per ASTM C133-7.
Each value of HMOR was the average of two parallel
specimens. It was done by three – point bending test using
HMOR testing apparatus. All the specimens for HMOR were
taken as 150mm × 25 mm × 25 mm without pre - firing at air
atmosphere. The final temperature of HMOR was 1400oC
with a heating rate of heating rate of 5oC/min. It was done
in air atmosphere with a soaking time of 30 min. Finally, the
loading rate of HMOR was 1.2-1.4 kg/s according to
samples.
 The HMOR value was calculated by the following formula:
𝟑𝐖 ∗ 𝐋
𝑯𝑴𝑶𝑹 =
𝟐𝐛 ∗ 𝒅𝟐
Where “W” (kg) is the maximum load when the specimen is
broken;
“L” is the span length between the lower supporting points.
(125 mm for all the tests in the work);
“b” is the breadth (cm), “d” is the height of the specimen (cm).
 h) Modulus of elasticity (MOE)  By determining the bulk density and ultrasonic velocity of a
 MOE was measured by the ultrasonic method in which the refractory material, it is possible to calculate the dynamic
propagation speed of ultrasonic waves was measured along modulus of elasticity using the equation below:
the length of tempered samples of 150×25×25 mm.
Ultrasonic pulse velocity testing (UPVT) was first reported
being used on refractory materials in the late 1950’s. Briefly, 𝐩𝑽𝒔𝟐 (𝑽𝒑𝟐 − 𝟒𝑽𝒔𝟐 )
𝑴𝑶𝑬 =
pulses of longitudinal elastic stress waves are generated by (𝑽𝒑𝟐 − 𝑽𝒔𝟐 )
an electro acoustical transducer that is held in direct contact
with the surface of the refractory under test. After travelling  From this we can also measure bulk modulus and shear
through the material, the pulses are received and converted modulus by using the following equations,
into electrical energy by a second transducer.
𝛒(𝑽𝒑𝟐 − 𝟒𝑽𝒔𝟐 )
𝑩𝒖𝒍𝒌′ 𝒔𝒎𝒐𝒅𝒖𝒍𝒖𝒔 =
 Most standards describe three possible arrangements for 𝟑
the transducers:
𝑺𝒉𝒆𝒂𝒓 𝒎𝒐𝒅𝒖𝒍𝒖𝒔 = 𝛒 𝑽𝒔𝟐

 Where VS is the pulse velocity (m/s), Vp is the shear velocity

1. The transducers are located directly opposite each (m/s) and ρ is the bulk density (kg/m3)
other (direct transmission).
i) Oxidation resistance
2. The transducers are located diagonally to each other;
 Oxidation resistance of the fabricated bricks was tested on
that is, the transducers are across the corners (diagonal
cube shaped samples. The samples were fired in an
transmission).
electrical furnace at 1400oC for 10 hours in air atmosphere.
At this temperature all the carbonaceous materials of the
3. The transducers are attached to the same surface and
brick got oxidized particularly from the outer surface. The
separated by a known distance (indirect transmission).
color of the oxidized portion turned off-white compared to
The velocity, V, is calculated from the distance between
the black color of the virgin brick and therefore the
the two transducers and the electronically measured
boundary between the un-oxidized and the oxidized regions
transit time of the pulse as, V (m/s) = L / T Where L is
were quite evident. After the heat-treatment, the cuboid
the path length (m) and T is the transit time (s).
shaped samples were cut and the diameter of black portion
 was measured at different locations and the average value
was taken.
 Oxidation index is determined by the formula:
𝐀𝐫𝐞𝐚 𝐨𝐱𝐢𝐝𝐢𝐳𝐞𝐝 𝐳𝐨𝐧𝐞
𝑶𝒙𝒅𝒏 𝒊𝒏𝒅𝒆𝒙 = ∗ 𝟏𝟎𝟎
𝐓𝐨𝐭𝐚𝐥 𝐚𝐫𝐞𝐚
 Lower oxidation index indicates the higher oxidation
resistance of the brick.
 It may be noted that conventionally the oxidation resistance
tests are carried out by firing the samples at 1400oC for 5
hours. However we have used a much more stringent test
standard for measuring oxidation resistance of our
specimens.
resistance. The quantification was done by the number of
cycles to withstand such temperature fluctuations. The
sample specimens were cut from tempered bricks. These
samples are heated at 1400°C for 10 minutes and then
suddenly brought down to ambient conditions by cooling it
in the air for 10 minutes. The number of cycles before any
crack in the specimen was noted down as the thermal shock
resistance.
Notes

j) Thermal shock resistance

 Thermal shock/thermal spalling is the direct result of
exposing the refractory installations to rapid heating and
cooling conditions which cause temperature gradients
within the refractory. Such gradients cause an uneven
thermal strain distribution through the sample, may cause
failure of the material. The standard method of finding out
spalling resistance is heating the material at an elevated
temperature followed by sudden cooling in air at ambient
temperature. The thermal shock resistance of refractory
materials is determined using standard quench tests in
which the material is heated and cooled subsequently and
the number of heating & cooling cycles that a material can
withstand prior to failure is taken as its thermal shock
 Structure and chemistry of
graphite and expanded graphite:
 An investigation of natural graphite was done by using
different experimental techniques like SEM and XRD.
Natural graphite was characterized were characterized from
the points of view of their particle size, crystallinity, purity
etc.

Chapter (5)
Results and Figure 29. SEM Image of natural graphite

discussion
 From SEM images it was observed that natural graphite is
flaky in nature and the graphene layers are attached
together. From the SEM images it was also observed that
the dimension of graphite flakes is more than 200 μm.

Figure.31: XRD pattern of graphite

 XRD patterns of natural graphite are presented in Fig.31.

From the XRD pattern it can be seen that there was some
silica impurities present already in the natural graphite. The
Figure 30 Thermal analysis of the natural flake graphite (97FC) peaks at 26.56 and 54.69o is consistent with the (002) and
sample. (004) peaks of graphite respectively.

 Thermal analysis was done in flowing air atmosphere up to a

temperature of 1000oC at 10oC/min. Results of TGA analysis  A detail characterization of expanded graphite was done by
of natural flake graphite samples are presented in Fig.30. As SEM, XRD and CHN test.
expected severe oxidation took place and consequently
weight loss occurred. However, the process was not
complete up to 1000oC (weight didn’t become constant).
Still from the graph we can have an idea that almost 85-90%
graphite was oxidized at that temperature range.
Figure 32: SEM images of expanded graphite
 From the SEM images of expanded graphite it was clear that
the natural graphite was expanded. After exfoliation the
graphite flakes are expanded perpendicular to the graphene
layers and gives a warm like structure. Spacing between the
graphene layers increased up to 30 μm and exposed.
 From the CHN test we also determined the carbon
percentage present in the expanded graphite. The result of
CHN test is given in the following table.
Table.6 weight % of CHN in expanded graphite

Sample name Carbon% Hydrogen% Nitrogen%

Expanded
73.56 4.47 2.14
graphite

Figure33: Thermal analysis of the expanded graphite

 Conditions of thermal analysis were same as the natural

graphite. Results of TGA analysis of natural flake graphite
samples are presented in Fig.33. The result is almost similar Figure.34: XRD pattern of expanded graphite
to the natural graphite. But the weight loss started at lower
temperature due to high reactivity of expanded graphite.
The oxidization process was completed around 900oC.
 XRD pattern of expanded graphite is similar to the natural
graphite except some extra impurity peaks which came due
to the presence of manganese oxide. There’s a lot of
difference in the peak intensities. Natural graphite shows a
great, sharp and symmetrical peak shape because of its high
crystallinity. After oxide intercalation, crystal defects
increase. As a result crystallinity decrease and diffraction
peak intensity decrease.
 The change in AP with the increase of expanded graphite is
shown in fig.35 .With the addition of expanded graphite the
percentage of AP is reducing. The AP varies in the range of
3.02 to 5 wt%. AP has the value of 4.07 wt% for B1 and has
the value 3.02 for B4. This decrease in AP is because of
addition of expanded graphite increases the filling of spaces
between bigger refractory particles. Thus overall the
porosity decreases. But in case of B5 expanded graphite AP
increases again.

Physical and mechanical properties

a) Physical properties
Bulk density %
i. Apparent porosity, Bulk density and Cold crushing 3.1
strength (before coking): 3.05
3.05
3
2.99
Apparent porosity% 2.95
2.95
2.97 Bulk density
6 2.9
2.91
5 2.85
5 2.8
4 4.35
4.07 B1 B2 B3 B4 B5
3
3.02 3.2 Apparent porosity
2 Figure 36: Variation of bulk density with the variation of
1 expanded graphite content
0
B1 B2 B3 B4 B5

Figure35: Variation of apparent porosity with the variation of

expanded graphite content
 The variation of bulk density is shown in fig.36. The variation  The variation of cold crushing strength with the expanded
of bulk density with the expanded graphite is very less which graphite is shown in fig.37. From the figure it is clear that
ranges from 2.91 gm/cc to 3.05 gm/cc. The bulk density for with the increase of expanded graphite cold crushing
B1 was 2.95 gm/cc. With the increase of expanded graphite strength increases. The CCS value of the sample which
content better pore filling is done which results in a higher contains no expanded graphite is 467 kg/cm2 but for B4
bulk density. But as the pore filling is done for B4 so, bulk sample CCS value is 609 kg/cm2. But the CCS value remains
density decreases again with further addition of expanded almost same after B4 sample. Increase in CCS is because of
graphite. the increase of expanded graphite which causes better
filling of pores and results in an increase in BD. But for B4
best pore filling is achieved. So, further addition of
expanded graphite does not affect the CCS value much.
Cold crushing strength (kg/cm2)
700
600
609 587
500
400 467 450
413 Cold crushing
300
strength
200
100
0
B1 B2 B3 B4 B5

Figure 37: Variation of cold crushing strength with the

variation of expanded graphite content
 ii. Apparent porosity, Bulk density and Cold crushing
strength (After coking): Coked bulk density (g/cc)
2.92

Coked apparent porosity% 2.9 2.91

2.88 2.89
16
14 2.86 2.87
2.86 coked bulk density
12 13.58 2.84
10 11.85 2.84
10.8 10.4 2.82
8 10.07 coked apparent
6 porosity 2.8
4 B1 B2 B3 B4 B5
2
0 Figure39: Variation of coked bulk density with the variation of
B1 B2 B3 B4 B5
expanded graphite content

Figure 38: Variation of coked apparent porosity with the

variation of expanded graphite content  The change in bulk density of coked bricks is shown in fig.39.
The values of bulk density vary from 2.84 gm/cc to 2.91
 The variation of apparent porosity of coked bricks is shown gm/cc. The values decrease in comparison with bulk density
in fig.38. With the addition of expanded graphite the of tampered bricks. This is because of the same reason of
percentage of AP is reducing in similar fashion to AP of the burn out of resin during coking. Similar to the previous tests
bricks before coking while B4 brick gives the best value. The here also the B4 brick shows the best value which is 2.91
AP varies in the range of 13.58 to 10.07. The coked AP value gm/cc.
of the B1 brick has increased more than other bricks. AP
values of coked bricks increase because of the burning out
of the total organic portion of the resin. Due to the burn out
of the resin pores are created within the bricks which
increase porosity.
 b) Mechanical properties
Coked cold crushing strength
(Kg/cm2) iii. Modulus of elasticity (MOE)

300
250 Modulus of elasticity (GPa)
200 239 225
206 60
150 174 190 coked cold crushing
100 strength 50
52.11
50 40 47.5 46.85
43.98
40.91
0 30 coked cold crushing
B1 B2 B3 B4 B5 strength
20

Figure 40: Variation of coked cold crushing strength with the 10

variation of expanded graphite content 0

 The coked CCS values are shown in fig.40 The CCS values of
coked samples vary in between 174 kg/cm2 to 239 kg/cm2.
From the figure it can be shown that the CCS values of
coked samples change in similar fashion with tempered
samples where B4 brick gives the best value. The CCS values
of coked samples are lowered because of the breaking of
the interlocking structure which has been created after
polymerization of phenolic resin. The breaking of the
interlocking texture was due to the burn out of the total
organic portion of the resin.
B1 B2 B3 B4 B5
Figure 41: Variation of modulus of elasticity with the variation
of expanded graphite content
 Fig.41. shows the variation of MOE with the variation of
expanded graphite content. With the increase of expanded
graphite percentage MOE decreases almost linearly. MOE
values vary within 40.91 GPa to 52.11 GPa. MOE value is
highest for the brick which contains no expanded graphite.
It is lowest for the B5 brick. As the amount of expanded
graphite increases compressibility of the bricks increases
which ultimately decreases the MOE value of the bricks.
 iv. Hot modulus of rupture (HMOR) values decrease with increase in expanded graphite from
69.14% to 40.48%. As expanded graphite forms carbide
 Comprehensive result is not given in this e-thesis for which has higher oxidation resistance property than that of
intellectual property issue. With the increase of expanded natural graphite so, the oxidation index decreases with the
graphite pores inside the bricks fill better. So, the strength increase of expanded graphite.
of the bricks enhances. Because of high surface area,
expanded graphite is more reactive than graphite. So, at the
high temperature, higher amount of carbide forms by
Notes
reacting with antioxidants with the increase in expanded
graphite.

v. Thermal shock resistance

 Comprehensive result is not given in this e-thesis for

intellectual property issue. Batch 1 shows a good result than
batch 2 and 3. Batch 2 and batch 3 shatter after 7th and 8th
thermal cycle, whereas the batch 1 sample shatters after 9th
thermal cycle. Batch 4 gives the best result which stands
12th thermal shock. But Batch 5 breaks at 12th thermal cycle.
Batch 4 and batch 5 shows better thermal shock resistance
than others because as the percentage of expanded
graphite increases so distribution of carbon into the entire
matrix increases.

vi. Oxidation resistance

 Comprehensive result is not given in this e-thesis for

intellectual property issue. The variation of the oxidation
index of the MgO-C bricks is clear. The oxidation resistance
of the brick increases significantly. The oxidation index
  Magnesia-Carbon refractory brick is one of the most
important refractories in the steel industry. Magnesia-
Carbon bricks have many advantages over the conventional
alumina brick lining or alumina / alumina spinel castable
linings.

 An attempt has been made to reduce the graphite content

of the MgO-C refractory by replacing a part of the graphite
by expanded graphite in this study. Effect of addition of
expanded graphite has been studied in this present work.
Total carbon content used for these bricks were 5 wt%.
Other raw materials used for this study were fused
Chapter (6) magnesia, antioxidants (Al and B4C powder) and resin binder
(both liquid and powder). The compositions were mixed and
pressed and then various refractory properties were

SUMMARY AND measured for both tempered and cured samples. The effect
of expanded graphite was studied by different
characteristics of the bricks and the properties were

CONCLUSION compared with the brick which contained no expanded

graphite under similar manufacturing conditions.

 The significant features of the new class of refractories

fabricated are as follows.

I. The newly fabricated MgO-C refractories exhibited

lower apparent porosity. Consumptions as compared to
the standard MgO-C refractory (with no EG). For these
two compositions, bulk density was also found to
increase marginally to 3.05 gm/cc from 2.95 gm/cc for
the standard brick.
 II. The new compositions exhibited a maximum of 20%
increase in the cold crushing strength relative to the
standard compositions.
III. Apparent porosity of the coked samples shows
progressive lowering in porosity with the amount of EG
used, although the coked porosity was lower than
uncoked. Additionally the coked bulk density was found
to increase than the standard composition.
IV. The trend of CCS for coked samples were similar to
those of uncoked samples with two of the new
compositions showing ~20% increase in coked CCS.
V. Two of the new compositions exhibited phenomenal
increase in HMOR. The increment was almost 80%
higher than that of the standard MgO-C refractory.
VI. The EG fortified bricks showed progressive decrease in
the value of MOE from ~50 to 40 GPa.
VII. The new formulations showed excellent thermal shock
resistance. While the standard brick failed at 9 air
quenching cycles, our composition went past 12 cycles.
VIII. Dramatic increase in oxidation resistance was observed
for the new compositions with an index of ~40% as
compared to ~70% for the standard composition.
 In totally we have formulated a low carbon MgO-C
refractory with 5% graphite with special carbon additives
that exhibits excellent thermo-mechanical properties as
noted above. Two of the compositions B2 and B3 had either
comparable or inferior properties as compared to the
standard composition. On the other hand, B4 and B5
exhibited dramatically improved thermo-mechanical
properties including HMOR, thermal shock resistance and
oxidation resistance.
 The technology demonstrated in this work is genetic to
carbon/graphite containing refractories in that many of this
class of refractories can be strengthened with this approach.
This opens up great opportunities to explore new and
improved refractory systems.
Scope of the future work
 This investigation has opened up a tremendous scope of
further research in this direction. The results so far obtained
are highly encouraging and may lead to detailed scientific
studies. Field trials should be carried out with this club of
MgO-C bricks in industrial operational condition. However,
the positive effect of addition of expanded graphite to MgO-
C refractory has been well-established in this study. A huge
potential exists for future commercial application of this
study to improve the properties of MgO-C refractories.
Notes

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