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Journal of Al-Nahrain University Vol.20 (1), March, 2017, pp.

78-86 Science

Studying the Effect of MgO Addition on the Thermal and


Electrical Properties for Iraqi Porcelain
Duraid Fawzi Mahdi
Department of Applied Science, University of Technology, Baghdad-Iraq.
E-mail: Duraid_fawzi2000@yahoo.com.

Abstract
The research was studied effect of addition Magnesium Monoxide (MgO) on the thermal and
electrical properties of Iraqi Porcelain with different weight percentages were (0%, 5%, 10%, 17%,
23% and 30%). The Porcelain was hard type and consist of (50%wt) Kaolin, (25%wt) Potassium
Feldspar and (25%wt) Flint and sieving process was achieved for all powders and the particle sizes
were (<125µm with 50%wt), (<75µm with 35%wt) and (<250µm with 15%wt) for Kaolin. The
other particle sizes were (<75µm) for Potassium Feldspar, (<75µm) for Flint and (<63µm) for
MgO. The powders were formed into disc shapes with diameters (10mm) and (40mm) by semi-dry
pressing with (3 ton) applied pressure and Glycine (organic material) was added to powders through
forming process with one drop to one gram from powder as a binder. The specimens were sintered
in electrical furnace of (1250OC) for (2 hrs) as soaking time with increasing rate 7OC for one
minute. The Bulk Density, Apparent Porosity, Specific Heat Capacity, Thermal Conductivity,
Thermo- Compressive Strength and Dielectric Strength were studied. The best results for Specific
Heat Capacity and Thermal Conductivity are F mixture with (30%MgO), Thermo- Compressive
Strength is E mixture (23%MgO) and Dielectric Strength is C mixture (10%MgO).
[DOI: 10.22401/JNUS.20.1.11]
Keywords: Traditional Ceramics, Advance Ceramics, Insulators, White wares, MgO and Porcelain.

Introduction were nepheline syenite, Talc, manganese


Porcelain is hard glazy white-ware made by dioxide, and barium carbonate have been used
a high temperature; generally consist of to produce porcelain insulators with 30%
refined main raw materials which are clays as alumina and then their electrical and
binders, feldspar as fluxes and flint as fillers. mechanical properties have been investigated.
Porcelain is used for both art and technical The results have shown that among used
fields with triaxial formation consist of 40- fluxes adding 1% barium carbonate increases
50% plastic base, 20-30% flux and 15-25% density to 2.7 g/cm3, bending strength to
filler [1]. In 2009, Akinori Nagasawa and etl. 1608 kg/cm2 and electrical strength up to
Were studied the addition of iron oxide to 33 KV. Besides mullite and corundum peaks
dental porcelain material with weight intensity when using 1% barium carbonate has
percentages from 0.6% to 5.0%. Slurry was been accomplished [7]. Currently three types
placed on human enamel and dental porcelain of porcelain are distinguished in Europe: Hard,
surfaces, Nd:YAG laser was exposed with Vitreous and Bone Porcelain [2].
varying energy and exposure time periods. Hard porcelain as a rule is made from a
Melting of material occurred with conditions; batch composition consisting of 50% clay
40 W for 4 s for 0.6% iron oxide, 20 W for 2 s material, 25% feldspar and 25% flint fired at
for 2.5% and 5% iron oxide. However (1250-1450OC). The fired body of hard
degradation of tooth substrate also was porcelain, which is composed essentially of
detected with high energy and extended mullite (Al6Si2O13), quartz and glass phase,
exposure period [3]. In 2012, Arman Sedghi exhibits a high transparency and high degree
and etl. Were made higher strength porcelain of whiteness. Hard porcelain resists melting
as insulator for power industry by decreasing for better than other kind of porcelain because
the Silica and increasing the alumina provides it is fired at higher maturation temperature [1].
a higher mechanical strength in porcelain. Vitreous porcelain differs from hard
They were used four types of fluxes which porcelain by its higher feldspar and quartz

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Duraid Fawzi Mahdi

content, resulting in lower firing temperature. Magnesium oxide (MgO, magnesia) occurs
Accordingly, the values of the properties of naturally as the mineral periclase, a
vitreous porcelain do not correspond to high metamorphic mineral formed by the
standard of hard porcelain. It was developed in breakdown of dolomite, CaMg(CO3)2, and
Europe in an attempt to imitate the Chinese other magnesium minerals. The principal
Hard Porcelain. Most of it is creamy-in tone, commercial sources of MgO are magnesite
and some people prefer this color to pure white (MgCO3) and magnesium hydroxide
[2]. [Mg(OH)2]. The major application for
Bone porcelain is characterized by higher magnesia is as a refractory lining in furnaces
transparency, creamy white color, high degree [1]. Magnesium oxide is very bulky white
of whiteness and good mechanical strength. As powder, known as light magnesium oxide [8].
a rule the batch composition consist of The density of MgO is 3.58 gm/cm3 and
20-50% bone ash, 20-45% Cornish stone and insoluble in water. The crystalline structure of
20-35% kaolin. The firing occurs in an MgO is face center cubic and melting point is
oxidizing atmosphere at (1200-1300OC) with 2852OC with good thermal shock resistance
short firing range and first firing step is the [9].
glazing. Because of the mixture composition
deformation occur relatively frequently during Experimental Work
firing [1]. The work in this research is divide to many
Fig.(1) shows how mechanical strength, parts which are shown in Fig.(2) and these
electrical strength and thermal shock parts are:
resistance depend on the composition of the
body. It is obvious that the best possible value Materials
of these three technically important properties The materials used in this research are:
cannot be attained in one and same body [4].
Physical appearance of hard porcelain is high Porcelain
quality, dense body, and continental hard- The type of Porcelain was used in this
paste white, vitrified translucent. The research is Hard Porcelain type and consisting
chemistry of hard porcelain is SiO2 (58- of following materials:
73 wt%), Al2O3 (18-36 wt%), K2O (1-8 wt%)
and CaO (0-4 wt%) [5]. Technical applications Kaolin
of hard porcelain are laboratory tools such as Kaolin clay is represent 50(wt%) from hard
crucible, filtering funnel, mortar and ball mill porcelain body and used to produce traditional
[6]. Electrical capacitors and insulators are ceramics when the color of the finished object
important applications for hard porcelain [5]. and its high temperature performance are
important. The mineralogical composition of
kaolinite (Al2O3 2SiO2 2H2O is 46.6 wt%
silica, 39.5 wt% alumina, and 13.9 wt% water)
due to the presence of impurities [10]. The
kaolin was used in this research is Iraqi Kaolin
from Alduejlh Zone.

Potassium Feldspar (Potash Feldspar)


Potassium feldspar is represent 25(wt%)
from hard porcelain body. Potassium feldspar
is a common name that applies to a group of
minerals with a general chemical formula of
KAlSi3O8 (K2O.Al2O3.6SiO2). Potassium
feldspar is usually white or very light in color
Fig.(1): Properties of Porcelain dependence
and has a hardness of 6 on the mohs' scale of
on rational composition [4].
hardness and has good cleavage in two
directions. The crystalline structure of

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Journal of Al-Nahrain University Vol.20 (1), March, 2017, pp.78-86 Science

potassium feldspar consists of an infinite kaolin fine powder, P.S. <75 µm for potassium
network of SiO2 and AlO4 tetrahedra and the feldspar fine powder, P.S. <75 µm for flint
mineralogical composition of potassium fine powder and P.S. <63 µm for MgO fine
feldspar can be expressed in term of the powder. The sieving process was running for
ternary system Orthoclase. Potassium feldspar 6 hours with discontinuous mode.
is primarily used in industrial applications for
their alumina and alkali content [11]. The Mixing Process
potassium feldspar is used in this research The total weight of sample is (20gm) and
from Alduejlh Zone too. the research is making six batches with
different addition of MgO which are (0 wt%,
Flint 5 wt%, 10 wt%, 17 wt%, 23 wt% and
Flint is represent 25(wt%) from hard 30 wt%). The weights and percentages of all
porcelain body. Flint has been used for the raw batches were used in this research are shown
material for tools longer than any other in Table (1). By using digital balance with two
material and fortunately it does not decay. digits, all different batches are weighs
Flint was formed in the chalk deposits; water according to weigh percentages of addition
percolated through the chalk and dissolved the MgO and mixed by manual porcelain mortar.
silicon molecules within the chalk. Flint is Through mixing process, an organic material
consists primarily of SiO2 43(wt%) and other powder is term "Glycine" with formula
oxides with different weight percentages such (NH2CH2COOH) was dissolving in distills
as Al2O3, Fe2O3, CaO, MgO, K2O, …etc [3]. water with ratio 1 gram glycine powder/ 4 ml
The flint was used in this research from distill water. It was added to all batches with
Bauxite location in the west desert of Al-Inbar ratio 1 drop/ 1 gram from batch as a binder
state. which helpful in forming process. The good
mixing is done when grinding and stirring is
Magnesium Oxide (MgO) be good and all the different powders are
Magnesium oxide or magnesia is a white interfering and become one powder with one
hygroscopic solid mineral that occurs naturally color as obvious for eye.
as periclase and is a source of magnesium. It
has an empirical formula of MgO and consists
of a lattice of Mg2+ and O2- ions held together
by ionic bonding. MgO a refractory material is
one that is physically and chemically stable at
high temperatures [9]. MgO was used in this
research is made by BDH chemicals Ltd
poole-England with purity 96%.

Crushing and Milling


The Iraqi flint, potassium feldspar and
kaolin stones are converting to powders by
using Retsch Jaw Crusher (Germany). Then
the small aggregates are converting to fine
powders by using porcelain ball mill (Baird &
Tatlock) (UK) with 22 porcelain balls for
24 hours in run with medium velocity.

Sieving Process
The fine powders are sieving in different
sieve sizes by using Retsch Sieving Machine
Germany made. The using particle sizes
are P.S. <75 µm (35 wt%), P.S. <125 µm
(50 wt%) and P.S. <250 µm (15 wt%) for Iraqi

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Duraid Fawzi Mahdi

Fig.(2): The block diagram of experimental work.

Table (1)
Batch Weights.
MgO Porcelain(weights gm)
Potash
Flint
Weight(gm) Kaolin (50 wt%) Feldspar
Batch (25 wt%)
wt% (25 wt%)
P.S.<125µm P.S.<75µm P.S.<250µm
P.S.<63µm P.S.<75µm P.S.<75µm
50 wt% 350wt% 15 wt%
A 0 0 5 3.5 1.5 5 5
B 5 1 5 3.5 1.5 5 5
C 10 2 5 3.5 1.5 5 5
D 17 3.4 5 3.5 1.5 5 5
E 23 4.6 5 3.5 1.5 5 5
F 30 6 5 3.5 1.5 5 5

Forming Process batch. The applied pressure was 3 ton under


The semi-dry pressing method was used by 15 sec. for all specimens.
manual hydraulic press and steel dies of
diameters 10 mm and 40 mm, 12 specimens Sintering Process
were produced with diameter 10 mm and By using Nabertherm furnace (Germany
weight of one specimen is 1.3 gm for one made), the rate of increasing temperature was
batch. One specimen was produced form 7OC/min to avoid the cracks that could be
diameter 40 mm with weight 5 gm for one happen throughout crystalline water vapored

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Journal of Al-Nahrain University Vol.20 (1), March, 2017, pp.78-86 Science

and phase transformations. Starting increasing equilibrium temperature that result. The heat
furnace temperature along process until reach absorbed by the water and the containing
to the 1250OC, the time was 2 hrs. The socking vessel can be calculated and this value equated
time was 2 hours and then the furnace was off to the expression for the heat given up by the
cooling to the room temperature. hot material. From this equation the unknown
specific heat capacity can be calculated [14]:
Bulk Density
Bulk density is defined as the mass (weight) ms. cps (Ts – T2) = mw . cpw ( T2 – T1) + mc . cpc
of the dry solids divided by the total volume of (T2 – T1) ........................ (4)
the wet sample; that is, bulk density is the ratio where ms is the mass of specimen (gm), cps is
of the mass of the mineral grains to the total specific heat capacity for specimen (J/gm.OC),
volume. All index properties are essentially Ts is temperature of heated specimen (100OC)
ratios of masses and volumes. Therefore, bulk before putting inside the calorimeter, T2 is
density can be calculated directly from mass final temperature after putting the heated
and volume measurements, or by relationships specimen inside calorimeter, T1 is the initial
with other index properties. The equation for temperature of water, mw is the mass of water
bulk density is [12]: (gm), cpw is the specific heat capacity of water
(4184 J/gm.OC), mc is the mass of calorimeter
...................................................... (1) (gm) and cpc is the specific heat capacity of
calorimeter (0.385 J/gm.OC).
Where bulk density (gm/cm3), M is is
mass of specimen (gm) and V is volume of
Thermal Conductivity
specimen (cm3).
Thermal conductivity is defined as the
property of a material's ability to conduct heat
Apparent Porosity
as a result of temperature difference under
It is a measure of the effective open pore
steady state boundary condition. Thermal
space in the ceramic body into which the
conductivity is determined by Lee’s Disc
water, liquid, gas and other solutions can
method which the specimen put between two
penetrate and thereby contribute to eventual
brass discs and the heater is supplied by
degradation of the structure. The porosity of
electric current from power supply. When the
ceramic body is expressed as the average
two temperature of the two brass discs are
percentage of open pore space in the overall
stable in certain temperature and do not
ceramic body volume. The specimens were
increasing over, the difference between two
immersed in pool of water for 24 hrs and their
temperatures is recording and thermal
weights were measured as wet weight, dry
conductivity is calculated from the following
weight and hanging weight in water in gram
[15]:
units. The equation for apparent porosity is
[13]: ( )
................................................ (2) ( ) ......... (5)
.................................... (3)
( ) ( )
where P% is apparent porosity, is exterior .................................. (6)
volume, S is wet weight of specimen (gm), I is
hanging weight of specimen in water (gm) and where K is thermal conductivity (W/m.OC),
D is dry weight of specimen (gm). TA, TB and TC are temperatures of A, B and C
brass discs, dA, dB and dC are thicknesses of
Specific Heat Capacity brass discs (mm), dS is thickness of specimen
The method of mixtures used in this test (mm), r is radius of brass discs (mm), I is the
method consists essentially a known mass of pass electric current (0.25 A), V is supply
material is heating at certain temperature and voltage (6 V).
put in a known mass of water which
temperature is low and determining the
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Duraid Fawzi Mahdi

Thermo-Compressive Strength decrease in bulk density actually; because of


Thermal shock was made for specimens in the bulk density of MgO (3.58 gm/cm3) is
different temperatures which are 100OC, higher than bulk density of hard porcelain
250OC and 450OC for 15 min stay in these (2.4 gm/cm3). Theoretically, the bulk density
different temperatures and cooling rapidly in of hard porcelain is increasing when weight
cold water with temperature 3OC for one time. percentage of MgO is increasing, but does not
After thermal shock was made the shocking occur because of increasing of porosity
specimens are put under load to test percentage with bulk density is more than
compressive strength and how the value of increasing of bulk density for hard porcelain,
compressive strength is become. Compressive especially at last three weight percentage of
strength is one of must use modifiers to be MgO. The some of MgO particles are interface
specific and it is mean the applied load on area with create glass phase through sintering
of cross-section of specimen and it is circle process and reaction is happen and restricted
certainly. The specimen is a cylindrical shape the diffusion of glass phase in whole hard
put under load with MPa units and the porcelain body. This is leave pores in some
equation of compressive strength is [13]: regions of hard porcelain body and increase
with MgO weight percentage.
...................................................... (7)

where σ is compressive strength in MPa unite,


F is load in N unite and A is area of circle in
m2 unite.

Dielectric Strength
Dielectric strength is a measure of the
maximum electrical field strength that a
material can withstand, after which electrical
(dielectric) breakdown occurs. The failure is
usually in the form of a carbonized puncture
through the material, and as a result the
material permanently loses its dielectric Fig.(3): The bulk density of hard porcelain
properties. The specimen with area 2 cm2 at with MgO wt%.
least and no more than 1 cm of thickness put in
pool of BAUR voltage breakdown tester- Apparent Porosity
England filling with viscos oil which has high As we seen in Fig.(4) which is prove our
dielectric strength between two pin of brass. pervious speak when increasing of MgO
The voltage breakdown tester is begin to weight percentage in hard porcelain body the
increase the voltage until to breakdown in value of apparent porosity is increasing
specimen is occur. The equation of dielectric obviously. This evidence on create the pores
strength is [16]: and increasing their percentage throughout
reaction with some of MgO particles which
.................................................... (8) decrease from movement of glass phase
diffusion in hard porcelain body through
where DS is dielectric strength in Kv/mm, V is sintering process. The wastes of MgO Particles
breakdown voltage in Kv and T is the are restricted fusion of hard porcelain
thickness of specimen in mm. constituents with each other because of small
particle size of MgO and high bulk density, so
Result and Discussion that the movement of atomic diffusion of hard
Bulk Density porcelain constituents and reaction with each
The increasing of weight percentage of other become more difficult. This lead to
MgO in the hard porcelain body lead to create more pores and vacancies in hard
decreasing in bulk density as shown obviously porcelain body.
in Fig.(3). But this case does not meaning
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Journal of Al-Nahrain University Vol.20 (1), March, 2017, pp.78-86 Science

Fig.(4): Apparent porosity of hard porcelain Fig.(6): Thermal conductivity of hard


with MgO wt%. porcelain with MgO wt%.

Specific Heat Capacity Thermo-Compressive Strength


Fig.(5) is indicating the increasing in value The increasing of MgO weight percentage
of specific heat capacity for hard porcelain addition due to increasing in compressive
when addition of MgO weight percentage is strength for three thermal declines (100-3OC),
increasing. This increasing is true, because of (250-3OC) and (450-3OC). The Fig.(7) is
the theoretical specific heat capacity of MgO indicating the increasing of compressive
with value (1.03 J/gm.OC) higher than the strength is not continuous; the increasing
theoretical specific heat capacity of hard of compressive strength is reach to certain
porcelain with value (0.92 J/gm.OC). The weight percentage of MgO addition. The
increasing is lead to increase in thermal thermal decline (100-3OC), the increasing of
potential energy of hard porcelain body with compressive strength value is reach to about
reduce in consumed energy for generated 17% from weight percentage of MgO addition
thermal. and after this weight percentage decreasing is
begins. In two thermal declines (250-3OC) and
(450-3OC), the increasing of compressive
strength value is reach to about 23% from
weight percentage of MgO addition and after
this weight percentage decreasing is begins
too. The reason of this case is increasing of
bulk density of hard porcelain when weight
percentage of MgO addition is increasing to
17% in thermal decline (100-3OC) and 23%
in two thermal declines (250-3OC) and
(450-3OC). Here the bulk density of hard
porcelain is stopping and apparent porosity is
Fig.(5): Specific heat capacity of hard
begin to increasing, so that the value of
porcelain with MgO wt%.
compressive strength is begin to decreasing for
hard porcelain.
Thermal Conductivity
The increasing of pore and vacancy
quantities which are result from increasing in
MgO weight percentage addition and lead to
decreasing in the value of hard porcelain
thermal conductivity as shown in figure
obviously. This case is increasing ability to
thermal insulation of hard porcelain and more
thermal saving with reduce of heat transfer by
conduction mode through hard porcelain body.

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Duraid Fawzi Mahdi

Conclusions
The addition increasing of MgO to hard
porcelain show improvement in the some
properties and certain limit to other properties:
1. Mullite which came from combination of
72% Al2O3 and 28% SiO2 and the Mullite
phase has good mechanical properties.
2. Quartz is other phase is creating through
sintering process above 1000OC and it is
crystalline form of silica and it has stable
physical and chemical properties at room
and higher temperatures.
Fig.(7): Thermo-compressive strength of 3. A few of Cristobalite is also create phase
hard porcelain with MgO wt%. in sintering process at 1250OC and another
form of silica with isostructural
Dielectric Strength polymorphs (cubic ice) and good thermal
The dielectric strength of hard porcelain is properties.
increasing when weight percentage of MgO 4. Glass phase is other create phase in
addition is increasing until reach to about 10% sintering process which is consist of
from weight percentage of MgO and after this combination of silica with other oxides
weight percentage the decreasing of dielectric and work as binder for hard porcelain
strength of hard porcelain is decreasing. As body lead to raise mechanical properties
shown in Fig.(8), the cause is belong to the of hard porcelain and reduce from pores
increasing of densification and reaction for and vacancies.
create glass phase throughout sintering process 5. Some particles of add MgO is reaction
in the spread regions of MgO particles. The with silica create phase of magnesium
densification and reaction with glass phase is silicates (MgSiO3) raising from
reducing and create percentage of pores and mechanical properties.
vacancies are become more after 10% from 6. MgO particles are reaction with glass
weight percentage of MgO addition. For this phase and made it more dense and viscos
reason, the dielectric strength of hard porcelain lead to raise bulk density and apparent
is decreasing because of the dielectric strength porosity in same time.
is inverse proportional to the create pores and 7. The rest of add MgO particles are become
vacancies in the ceramic body generally and waste in hard porcelain body causing
hard porcelain particularly. increasing in pores and vacancies.
8. The research is show the best batches
which are F (30 wt% MgO) for thermal
conductivity and specific heat capacity
properties, E (23 wt% MgO) for thermo-
compressive strength property and C (10
wt% MgO) for dielectric strength
property.
9. It is possible to use other additives such as
CaO, Cr3O, SiC, TiO2, ZrO2, Chromite
(FeO.Cr2O3) in order to development and
improvement the thermal and electrical
properties for hard porcelain.
Fig.(8): Dielectric strength of hard porcelain
with MgO wt%.

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Journal of Al-Nahrain University Vol.20 (1), March, 2017, pp.78-86 Science

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