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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
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REFRACTORIES
Introduction:
Refractory materials must be strong at high temperatures, resistant to thermal shock,
chemically inert, and have low thermal conductivities and co-efficient of expansion.
Refractory material may be defined as any material can with stand high
temperatures, without undergoing any softening or deformation in shape. They are also
expected to resist the abrasive and corrosive action of molten metals.
Classification:
Refractory materials are classified into three types based on their chemical properties.
1. Acid refractory: Refractory materials made up of acidic materials, which are
resistant to acidic substances at very high temperature. However they are reactive
to basic substances at high temperature.
Ex: Alumina (Al2O3), Silica (SiO2), Fireclay (25% Al2O3 and 75% SiO2) etc
2. Basic refractory: Refractory materials made up of basic materials, which are
resistant to basic substances at very high temperature. However they are reactive to
acidic substances at high temperature.
Ex: Magnesite (85% MgO+5.5% SiO2+ 2.5% CaO), Forsterite (2MgO.SiO2) and
Doloamite (CaMg (CO3)2.
3. Neutral refractory: Refractory materials made up of amphotaric/slightly
acidic/basic materials, which are resistant to strong acidic and strong basic
substances at very high temperature.
Ex: Carborundom (silicon carbide), Graphite, Chromite (FeO.Cr2O3) etc.
Characteristics:
i.
They should not undergo any physical, chemical and mechanical properties when
subjected to high temperature.
ii.
They should be chemically inert towards corrosive gasses, molten slag, produced in
furnaces.
iii.
They should posses good thermal properties, especially when subjected to thermal
shock.
iv.
They should withstand load at high temperature and rough operating conditions.
v. They should have uniform expansion and contraction upon heating and cooling to
very high and very low temperature.
Properties of Refractory:
1. Refractoriness:
It is the ability of a material to withstand heat, without undergoing appreciable
softening or deformation under particular working conditions.
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
It is usually measured as the softening temperature of the material, since most of the
refractory materials do not have sharp meting point, due to mixture of several oxides. The
softening temperature of refractory materials is usually determined by Pyrometeric Cones
Test method.
Measurement: Refractoriness is determined by comparing the behavior of cone of the
standard material upon heating, with that of the test material. The refractoriness is
expressed in terms of Pyrometric Cone Equivalent (PCE) values. These cones are small
pyramid shaped 38 mm height and 19 mm length with a triangular base, as shown in the
figure 1 below. When gradually heating, these cones start to deform (getting softened. The
temperature at which the fusion of the refractory test cone occurs is indicated by its apex
touching the base. The PVE value of the given refractory is taken as the number of the
standard cone, which fuses at the same temperature of the test cone. In case, if it fuses in
between, the average is taken.
Inside furnace
FURNACE
Deformed cone
35
36
37
Apex of the
cone touching
the base
Softening Temperature
1710 C
1800-1850 C
1850C
The refractory materials should possess high mechanical strength, even at high operating
temperature, to bear the maximum possible load, without breaking. Generally, softening
temperature decreases with increase of load. The load bearing temperature of a refractory
can be measured by the RUL test.
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
RUL test: It is performed by applying a constant load (3.5 to 1.75 kg/cm-2) of the refractory
specimen (of size 5 cm2 and 75 cm height) and heating in a furnace at a standard rate (10
C/min). The record of the height of the specimen versus temperature in measured.
The temperature at which the refractory deforms by 10% is called refractoriness
under load (RUL).
A good refractory material should high RUL, (high mechanical strength).
3. Dimensional stability:
It is the resistance of a material to any volume change, which may occur on its exposure to
high temperature over a prolonged time. The dimensional changes may be reversible or
irreversible. The irreversible changes will result in permanent contraction or expansion of
a refractory material. The irreversible contraction is due to the formation of fusible
constituent of the refractory when it is subjected to long period at high temperature. The
liquid gradually fills the pores and causing a high degree of shrinkage.
A good refractory material should have high dimensional stability or it should expand or
contract to the same extent upon heating and cooling.
4. Chemical inertness:
Thermal spalling is the property of breaking, cracking or peeling off of a refractory material
under high temperature.
A good refractory must show a very good resistance top thermal spalling. The reasons for
spalling are due to (a) Rapid change in temperature (b) Slag penetration.
6. Porosity:
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
Disadvantages:
It reduces the strength.
It reduces abrasion strength
It reduces the corrosion resistance
Advantages:
Highly porous refractory possess lower thermal conductivity. This is due to the
presence of more air voids, which act as insulators, and hence it can be used for
lining furnaces, ovens.
Highly porous refractory reduces thermal spalling.
Question bank:
1)
2)
3)
4)
5)
What are refractory materials? How are they classified? Give examples. ( 5 marks)
What are the requisites of a good refractory material? ( 2 marks)
Give an example for acidic, basic and neutral refractory. (3 marks)
Write note on characteristics of refractory materials. (4 marks)
What is refractoriness of a refractory material? Explain the determination
refractoriness based on pyrometric cone test. (6 marks)
6) Explain briefly the Refractoriness Under Load property of refractory. (3 marks)
7) Discuss the dimensional stability and chemical inertness of property refractory
material. (6 marks)
8) What is thermal spalling? Mention the reasons for the same. (4 marks)
9) Explain the advantages and disadvantages of porosity of a refractory material. (4
marks)
10) Write a short note on pyrmetric cone equivalent and thermal spalling. (6 marks)
11) Fill up the blanks in the following:
i)
Refractory material is defined as
ii)
Acid refractories should not be used in contact withwhereas
basic refractories should not be used in contact with .
iii)
Porosity of a refractory material is given by the ratio of ..
iv)
Thermal spalling means..
v)
The dimensional stability of refractory indicates.
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
NANOMATERIALS
What are nanomaterials?
Nano-scale materials are defined as a set of substances where at least one dimension is less
than approximately 100 nanometers. A nanometer is one millionth of a millimeter
approximately 100,000 times smaller than the diameter of a human hair. Particles with a
size between 1 and 100 nm are normally regarded as nanomaterials.
Classification of Nanomaterials
Nanomaterials have extremely small size which having at least one dimension is 100 nm or
less.
1) 1-Dimentional Nanomaterials: These can be nanoscale in any one dimension.
Ex: Surface films, Layers, plates shaped nanomaterials
2) 2- Dimensional Nanomaterials: These can be nanoscale in two dimensions.
Ex: Strands or fibres, Belts shaped nanomaterials
3) 3- Dimensional Nanomaterials: These can be nanoscale in three dimensions.
Ex: Particles.
They can exist in single, fused, aggregated or agglomerated forms with spherical, tubular,
and irregular shapes. Common types of nanomaterials include nanotubes, dendrimers,
quantum dots and fullerenes etc.
Applications of nanomaterials:
Energy:
1) Hydrogen storage materials synthesized at nanoscale have high H2 storage capacity. Ex:
Carbon nano tubes , Metal hydrides (MgH2, CaH2, LiAlH2 etc)
(The Hydrogen Economy offers a potential solution to satisfying the global energy
requirements while reducing (and eventually eliminating) carbon dioxide and other
greenhouse gas emissions and improving energy security. Hydrogen is a very attractive
alternative energy vector)
2) Nanomaterials for batteries :LiFePO4
3) Nanomaterials for solar cells: ZnO, TiO2, Thin film of Si, CdSe, CdTe etc
Environmental:
1) Electrochemical sensors based nanomaterials (Fe2O3, SnO2, ZnO, silica, carbon
nanotubes,) for environmental monitoring/sensing CO2, NOx, CO gasses.
2) Nanocrystalline MgO, CaO, TiO2 and Al2O3 adsorb polar organics such as aldehydes and
ketones, industrial waste etc
3) Nanocrystalline metal oxides are highly effective adsorbents towards a broad range of
environmental contaminants ranging from acids, chlorinated hydrocarbons,
organophosphorus and organosulfur compounds to chemical warfare agents. These
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
materials do not merely adsorb, but actually destroy many chemical hazards by
converting them to much safer byproducts under a broad range of temperatures.
Ex: TiO2 based nanomaterials for photo catalytic dye degradation.
Electronics:
The most revolutionary application in nanotechnology is in the semiconductor area.
Electrically conducting nanowires are developed by lithography; which reduces the size
and increases the conductivity of electrical contacts; The width of the nanowire can be
controlled by the size of the cluster that is chosen.
The decrease in size and increase in efficiency of Computers, Laptops, LEDs, Mobile phones
etc is result of usage of nanomaterials in their construction. Ex: use of nanotechnology in
the design of printed circuit boards (PCBs)
Medicine:
The use of nanotechnology in medicine and more specifically drug delivery is set to spread
rapidly. Currently many substances are under investigation for drug delivery and more
specifically for cancer therapy.
Ex: Nanostructured silica materials, carbon nanotubes, grapheme oxide etc.
Catalysis:
Nanomaterial-based catalysts are usually heterogeneous catalysts. The extremely small
size of the particles maximizes surface area exposed to the reactant, allowing more
reactions to occur.
Ex: Nano TiO2 for photocatalytic activity dye degradation, Co/ZrO2 catalysts in CO
hydrogenation, Nano MgO, CaO for biodiesel production, etc.
Synthesis of nanomaterials
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
500 C
The amount of fuel can be calculated in such way that the total oxidizing valency of fuel
should match with the total reducing valency of metal nitrate. The following formula can be
used to calculate the amount of fuel:
Wt. of fuel
x Valency of fuel =
Mol. Wt. of fuel
For the calculation of valency of fuel and metal nitrate, the valency to be considered for the
elements such as of N, O, H, C, and Mn+ are 0, -2, +1, +4 and +n respectively.
Procedure:
Step1: Weighing and mixing of the reactants:
Weighing of all the reactants (metal nitrate and a fuel) according to
stoichiometry, by using the above formula and dissolved in minimum
quantity of distilled water in a beaker of suitable size.
The mixture is stirred on a magnetic stirrer till to get uniform solution
as shown in figure (left side).
Magnetic stirrer on which uniform
redox solution is obtained by stirring
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Compiled by:
C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
Spontaneous/vigorous
combustion occurs and
propagates
throughout the redox
mixture
Evaporation
(boiling) of water
Compiled by:
C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
Example:
Synthesis of MgO by combustion method:
Chemicals: Magnesium nitrate (Mg(NO3)2.6H2O, (Mol. Wt=256.41) any organic fuel (say
urea; NH2CONH2; Mol. Wt = 60) and distilled water.
Instruments/Glassware: High Temperature Furnace, 250ml Borosil glass beaker, Tong,
Spatula, Weighing balance, Magnetic stirrer.
Calculation of fuel:
The valency of urea, N2H4CO= 2(0)+4(+1)+1(+4)+1(-2)= 6
The valency of Mg(NO3)2.6H2O= 1(+2)+2(0)+ 6(-2)+6(0)= 10
The amount of urea for 5.0 g of Mg(NO3)2 is calculated as follows.
Wt. of urea
x Valency of urea =
Mol. Wt. of urea
Wt. of Mg-nitrate
x Valency of Mg-nitrate
Mol. Wt. of Mg-nitrate
Procedure: weigh exactly 5.0g of Magnesium nitrate and 1.95 g of urea (1:1 stochiometry)
in 250 ml beaker and dissolve the salts by adding minimum quantity of distilled water and
stirring on a magnetic stirrer for 10 min. The uniformly dissolved redox mixture is kept in a
pre-heated furnace maintained at 500 C. The redox solution undergoes evaporation and
finally results in viscous-gel containing uniformly mixed magnesium nitrate and urea. After
some time it catches fire with the liberation of gases and heat energy, finally results in
highly porous, white powder of nano MgO. The nano characteristics formed powder is
further confirmed by using powder X-ray diffraction technique (crystalline phase),
Transmission Electron microscope (nano size).
Exercise:
Calculate the wt of fuel and write the combustion procedure for the synthesis of
1) ZnO from Zn(NO3)2.6H2O ( Mol. Wt. =297.49) using glycine (NH2CH2COOH, Mol. Wt =75)
2) CaO from Ca(NO3)2.4H2O ( Mol. Wt. =236.15) using glucose (C6H12O6= Mol. Wt =180)
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
2. Sol-gel method
It is a wet chemical technique widely used for the fabrication of nano-structured ceramic
materials and thin films.
Sol-gel process involves the conversion of precursor solution (usually metal salts or metal
alkoxide) into a nano-structured inorganic solid through inorganic polymerization reactions
catalyzed by water.
In general, metal alkoxides (M-OR) are widely used as precursors, because they readily
react with water.
The reactions involved in the sol-gel process are
(i) Hydrolysis
M-OR + H2O
Metal alkoxide
(ii) Condensation
M-OR + H O-M
M-OH + ROH
Metal hydroxide
M-O-M + R-OH
results in to a
Process:
Step 1: Preparation of homogeneous solution either by dissolution of metal salt in water or
metal alkoxide in an organic solvent (usually alcohol) that is miscible in water.
Step 2: Sol formation by hydrolysis
It involves the conversion of homogeneous solution into a sol. (A stable dispersion of
colloidal particles of precursors in a solvent is known as sol) due to hydrolysis reaction.
During hydrolysis, the alkoxide groups (-OR) are replaced via the nucleophilic attack of the
oxygen atom of a water molecules, results in release of alcohol and formation of metal
hydroxide (sol).
Step 3: Gel formation by condensation
The colloidal solution is kept for aging. During aging condensation reaction between two
metal hydroxyl/alkoxy species leads to M-O-M bonds with the release of H2O/R-OH. This
condensation process continues and finally results in a gel, an interconnected, a rigid and
porous inorganic network covered completely with liquid phase. This transformation is
called Sol-Gel transition.
Step 4: Drying of gel:
It involves removal of liquid phase from gel network. There are different ways of drying
gel:
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
(a) If the gel medium is dried, by removing the liquid solvent (under hyper critical
conditions) without destroying the gel network, aerogel is produced.
(b) If the solvent is dehydrated by under ambient conditions (removal of R-OH groups),
xerogel are produced.
(c) If the gel network is sintered at high temperature (800C), densification,
decomposition of gel results in complete collapse of gel net into powder.
Schematic representation of sol-gel process
Homogeneous aqueous
solution of metal
salt/alkoxide (in
alcohol)
Vigorous
Stirring
Formation of sol
(colloidal particles)
due to hydrolysis
reaction
undisturbed
gel network
covered with
only air
Supercritical
drying
Aerogel
Formation of Gel
(inorganic polymer
network) due to
condensations
reactions
Drying
condition
at ambien t
Xerogel
Sintering at 800 C
Powder
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
(1)
Ti
Hydrolysis
Ti
Titanium isopropoxide
+ H2O
O
Isopropanol
(2)
Ti
Ti
Ti
O
H
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Compiled by:
C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Ti
Ti
O
O
1. It is a simple and economic technique, as the fabrication does not need expansive
machinery or apparatuses.
2. It offers a high flexibility as one can produce materials with a wide range of
stoichiometry and additional dopants.
purity.
5. Nanomaterials of variety of shapes can be prepared.
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C. Manjuna tha , Assistant Professor, Depa rtment of Chemis try, R.V. College of Engineeri ng
Question bank:
1. What are nanomaterials? How are they differing from the bulk particles? (3
marks)
2. Explain the classification of nanomaterials. (3 marks)
3. Mention the applications of nanomaterials. ( 4 marks)
4. Explain the principle and procedure involved in the combustion synthesis of
nano structured metal oxide. (6 marks)
5. Mention the advantages of combustion method. (4 marks)
6. Calculate the amount of urea (NH2CONH2, Mol wt=60) required for the
complete combustion of 2.5g of Zn(NO3)2.6H2O ( Mol. Wt. =297.49) in to ZnO.
( 4 marks)
7. Describe the combustion synthesis of nano powder of CaO. ( 6 marks)
8. Explain the reactions and steps involved in sol-gel synthesis of nano
structured material. (6 marks)
9. With a neat diagram explain the sol and gel formation in sol-gel method.(4
marks)
10. Explain the preparation of nanostructured TiO2 using titanium isopropoxide
by sol-gel method. (6 marks)
11. Mention the advantages of combustion method. (4 marks)
12. Metal nitrates can be used as a metal precursor in combustion and as well as
sol-gel method, but metal halides cont be used in both. Give reason.
13. Fill up the blanks in the following:
i)
The metal precursor in combustion method should be.
ii)
Combustion synthesis is a redox exothermic reaction between metal
nitrate and
iii)
Hydrolysis of metal alkoxide yield.
iv)
Gel is a inorganic polymer network formed by .
reaction of metal hydroxide.
v)
.. is used as a nucleophile and catalyst in sol-gel
method.
vi)
Aerogel is formed the gel is subjected to extraction.
vii)
Xerogel is described as
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