Silicon (2019) 11:579–592

https://doi.org/10.1007/s12633-018-9963-4

ORIGINAL PAPER

Dielectric Properties of Basaltic Glass and Glass-Ceramics: Modeling

and Applications as Insulators and Semiconductors
G. A. Khater1 · B. S. Nabawy2 · J. Kang3 · M. A. Mahmoud1

Received: 26 May 2018 / Accepted: 26 July 2018 / Published online: 2 August 2018
© Springer Nature B.V. 2018

Abstract
Sinai basaltic rocks were melted as glass and casted into disc- and rode-shapes and subjected to thermal treatment to
induce crystallization as a glass-ceramic. The dominant crystalline phases were assigned as diopside, with some amounts of
anorthite and magnetite crystals. Different techniques were used in that study such as differential thermal analysis, X-ray
diffraction, SEM and dielectric properties (dielectric constant and loss beside to the electric conductivity). Glass-ceramic
samples that were thermally treated at low temperatures (850 ◦ C) gives surface crystalline and coarse-grained textures, while
glass-ceramic samples treated at relatively higher temperatures (1000 ◦ C) introduced volume crystalline and fine-grained
textures. The dielectric constant (ε ) was measured at 1000 points in the frequency range 42 Hz up to 8MHz. It decreases
with increasing the applied frequency and decreases with increasing the crystallization degree, where it varies between 9.99
at 42 Hz and 7.61 at 8 MHz. The dielectric loss values are relatively low (0.68 at 42 Hz down to 0.03 at 8 MHz), whereas
the electric conductivity (σ ) values refer to insulator materials (σ <10−8 S/m) at low electric frequencies at 42 Hz and to
semiconductor materials at high electric frequencies at 8 MHz (10−8 <σ <103 S/m). The results show that the glass-ceramic
can be used in low dielectric materials in the electronics covering industry.

Keywords Basalt · Dielectric properties · Glass · Glass-ceramic · Crystallization

1 Introduction for cleaning purposes of industrial gas emissions without

Basalt rocks are widespread volcanic rocks brought to the
surface through lava flows and eruptions. Basalts have many
applications as pavement rocks for the historical roads and
as aggregates for paving the high ways. The vesicular and
fractured basalts have been known for many decades as
hydrocarbon reservoirs and underground water aquifers [1, 2].
Recently, additional application of basalts is in the
form of basalt fibers which have been widely used for
heating purposes and sound insulation [3–5]. In addition,
due to their high thermal stability, basalt fibers are used
 G. A. Khater
j.khater@yahoo.com
1 Glass Research Department, National Research Centre,
Cairo, Egypt
2 Department of Geophysical Sciences, National Research
Centre, Cairo, Egypt
3 School of Materials Science and Engineering, University
of Jinan, Jinan 250022, China
preliminary cooling [6]. By the advance of the multimedia
applications and electronic industries, it became necessary
to reduce the weight of the electronic devices, to be
miniaturized, and greatly efficient. Therefore, the role of
microwave apparatus is becoming important for giving
out large-capacity information. There is a considerable
amount of microwave apparatus, such as GPS (global
positioning system; 1.5 GHz), WLAN (wireless local
area network), cell-phones (0.9:1.8 GHz), Bluetooth (2.4
GHz) and satellite communications (dozen of GHz) [7,
8]. Glass-ceramics can be used in multifunctional ceramic
substrates with high strength, adequate dielectric constant,
and low coefficient of thermal expansion. Therefore, glass-
ceramics are among the best materials that have the required
properties, where their dielectric and mechanical properties
can be simply controlled and enhanced. In general,
low-temperature co-fried ceramic (LTCC) materials are
separated into two groups: substrate materials with low
dielectric constants (below 10); and a set of capacitor
materials that are appropriate for multifunction and have
moderate to high dielectric constants [9]. There have
580
been numerous studies on low temperature fired ceramic
substrate materials in the next systems: MgO–Al2 O3 –SiO2
glass [10], alumina–lead borosilicate glass [11], and La2 O3 –
B2 O3 –TiO2 [12].
A study has been carried out on the CaO–MgO–SiO2
glass system revealed that the glass-ceramic substrate has
low dielectric loss and high strength values [13]. The
CaO–Al2 O3 –SiO2 system has been newly reported to have
adequate dielectric constant and good chemical durability
and low coefficient of thermal expansion [14]. Anywise,
the dielectric properties and the mechanical properties are
affected by the low crystallinity and high porosity of the
glass-ceramic materials. The mechanical characteristics and
dielectric properties of glass-ceramic materials, which have
complex microstructures, should be controlled by the degree
of the mineral crystallization of their main components.
The satellite and microwave telecommunication and
transmission industries have pronounced fast progress
through portable telephones. The dielectric components
should also be miniaturized to decrease the device size. In
latest years, low-temperature co-fired ceramics have been
developed to raise the volume competence by integrating
passive apparatus such as resistors, capacitors, and inductors
[15, 16]. The dielectric constants of trade low dielectric loss,
low-temperature co-fired ceramics materials are generally
between 4 to 9 [17].
The CaO-MgO-Al2O3-SiO2 glass system has attracted
much attention due to its low densification temperature, low
Thermal Expansion Coefficient (TEC <5 x 10−6 / ◦ C), low
dielectric constant (ε <10) and better chemical durability
[18]. To ease crystallization in CaO-MgO-Al2 O3 -SiO2
glass, dissimilar nucleating agents, for instance CaF2 , TiO2 ,
and ZrO2 , have been reported [19, 20].
Due to the appropriate dielectric properties of the basalt
rocks, the present study introduces a new application for
the basalt rocks for electric insulators and semiconductors
purposes (insulators <10−8 S/cm <semiconductor <103
S/cm <conductors) and as alternatives for substrates. To our
knowledge, the present study is the first study concerned with
the electric properties of the Egyptian basalts at differ-
ent frequency levels. The dielectric properties including the
dielectric constant and loss as well as the electric con-
ductivity were measured for some basalt flows widespread
in Sinai Peninsula in Egypt. Prior to the measuring pro-
Table 1 Chemical composition of the investigated glass sample
Calculated Chemical Composition (mol %)
SiO2 Al2 O3 Fe2 O3 TiO2
54.86 11.11 4.86 1.39
Silicon (2019) 11:579–592
cess, the basalt samples were molten and formed as glass
and glass-ceramic basalt. The wide range of the studied
dielectric properties of the studied basalts may introduce the
present study as a development for characterizing precisely
the properties of basalts and adds a new application for the
basaltic glass and glass-ceramic as electric insulators and
semiconductors. The present paper characterizes the dielec-
tric properties of the basaltic glass and glass-ceramic using
alternating electric field through a wide range of frequen-
cies, extending from 42 Hz up to 8 MHz. It investigates the
effect of crystallization progress and glassy matrix on the
dielectric properties.
2 Experimental Procedure
2.1 Basalt Melting and Glass Preparation
Some basalt samples have been collected from the western
coast of Sinai, crushed and milled for a while in an agate
mill till reaching very fine powder size that was sieved to
obtain particles less than 75 μm sizes. The obtained powder
samples were then mixed up to get an average sample
which is more representative for chemical composition of
the Sinai basalts. Chemical analyses were carried out for the
obtained basalt powder by using X-ray Fluorescence (XRF).
The prepared mixed-up batch sample was then melted in
alumina crucible at 1350 ◦ C to 1450 ◦ C for 2 hours to
obtain a homogeneous and a bubble-free glass. After that,
the bubble-free melt was casted onto a steel plate in the
form of very thin disc samples (4.0 mm thickness and 2 x 2
cm dimensions of two parallel surfaces to avoid irregularity
in thickness), and then transferred to a preheated muffle
furnace adjusted at 550 ◦ C, which was then switched off to
cool gradually to room temperature.
Table 1 shows the chemical composition of the inves-
tigated glass samples. The prepared glass samples are
referred as (1-B1), whereas the other processed and reman-
ufactured samples as glass-ceramics were referred as (2-B1)
thermally-treated at 850 ◦ C, (3-B1) thermally-treated at
900 ◦ C, (4-B1) thermally-treated at 950 ◦ C and (5-B1, pol-
ished sample to detect the effect of polishing on the obtained
results) thermally- treated at 950 ◦ C (non-polished), and
(6-B1) thermally-treated at 1000 ◦ C.
CaO MgO Na2 O K2 O
11.11 12.51 3.47 0.69
Silicon (2019) 11:579–592
2.2 Differential Thermal Analysis (DTA)
The Differential Thermal Analysis (DTA) scan of about 60
mg of a powdered glass sample (0.20 mm ≤ grain size
≤ 60 mm) was applied with Al2 O3 powder as a reference
material using a Perkin-Elmer Micro differential Thermo-
analyzer. The analysis was applied at a heating rate of
20 ◦ C/min and sensitivity of 8μV/cm for all the DTA runs
that were performed in ambient conditions and pure flowing
N2 (flowing at a rate of 30 cc/min). The DTA technique is
used as a guide for the temperature range that applied for
crystallization of the glass-ceramic samples.
2.3 Thermal Treatment
Thermal treatment was applied in a muffle furnace from
room temperature up to temperatures of 1000 ◦ C at 50 ◦ C
intervals with a heating rate of 10 ◦ C/min based on DTA
results as shown in (Fig. 1). Soaking times for 2 hours were
applied to start from the time at which the sample reached
the desired temperature. Choosing the soaking time is based
on the optimum time required to induce the crystallization
process in this type of glass. After soaking time, the furnace
was switched off and the samples were kept cooling inside it
down to the room temperature. A double stage heat treatment
was applied to study its effect on the obtained mineral
phases and microstructure, where the glass samples were first
soaked at 700 ◦ C for 1 h (for sample 1-B1) then at 850 ◦ C
(for sample 2-B1), 900 ◦ C (for sample 3-B1), 950 ◦ C (for
samples 4-B1 and 5-B1) and 1000 ◦C (for sample 6-B1) for 2h.
Fig. 1 Differential Thermal
Analysis (DTA) of the
investigated glass
581
2.4 X-ray Diffraction Analysis (XRD)
Diffraction patterns were acquired from the heat-treated
glass samples by Philips PW1390 type diffractometer
with Ni-filtered Cu-Ka radiation. All device settings were
maintained and matched for all analysis using a Si disc as
an external set; this was required to make the measurements
based on the peak height more accurate.
2.5 Scanning Electron Microscopy (SEM) Studies
The microstructure of the crystalline samples was studied
using scanning electron microscopy (SEM) of model XL30,
Phillips. Some representative fresh broken samples were
etched chemically by 1% HF+ 1% HNO3 solution for 1s.
The samples were then dehydrated and coated with a gold
film for SEM imaging.
2.6 Dielectric Measurements
The samples were introduced into a ceramic holder for
non-polarizing electrodes (resistivity less than 0.5 ohm)
linked to a highly precise and computerized IM3536 LCR
Hitester Hioki impedance bridge. The capacitance effect
(Cp), the electric resistivity (Rp) and the electric loss
tangent (D) were measured in a parallel arrangement by
sweeping through a full range of frequency at 1000 points
of measurements (at frequencies ranging from 42 Hz up to
8 MHz) at ambient conditions. The dielectric constant (ε ),
the dielectric loss (ε  ) and the electric conductivity (σ ) of
582 Silicon (2019) 11:579–592

Table 2 X-ray diffraction (XRD) of the investigated glass samples heat treated at different temperatures

Sample No. Heat treatment (◦ C, h) Phases developed Calculated phases developed (wt%) in samples 3-B1 and 6-B1

Diopside Anorthite Magnetite

1-B1 No treatment amorphous glass

2-B1 850 ◦ C, 2h diopside, anorthite, magnetite
3-B1 900 ◦ C, 2h diopside, anorthite, magnetite 55.0% 28.5% 16.5%
4-B1 950 ◦ C, 2h diopside, anorthite, magnetite
5-B1 950 ◦ C, 2h diopside, anorthite, magnetite
6-B1 1000 ◦ C, 2h diopside, anorthite, magnetite 66.6% 18.3% 15.1%

the basaltic glass and glass-ceramic basalt samples were
calculated as follows.
Cp × L
ε =
A × εo
where, Cp is the measured electric capacitance in parallel,
L (4 mm) is the sample thickness, A is the surface area of
the measuring electrode (22.07 mm), and εo is the dielectric
constant of the air (8.85 x 10−12 F/m).
ε = ε × D
Where; ε is the dielectric loss and, D is the measured
electric loss tangent (tan δ).
L peak indicates a wide temperature range through which
σ =
A × RP
where, σ is the electric conductivity, RP is the measured
electric resistance in parallel, L (4 mm) is the sample
thickness, and A is the surface area of the measuring
electrode (22.07 mm).
The obtained electric properties for the different samples
were found to increase incrementally with the increase of elec-
tric frequency in the applied range from 42 Hz up to 8 MHz.
(1)
3 Results
XRF analysis showed that the basaltic rocks samples is
composed mostly of SiO2 (54.86 %), Al2 O3 (11.11 %),
Fe2 O3 (4.68 %), CaO (11.11 %), MgO (12.51 %), Na2 O
(2) (3.47 %) and TiO2 (1.39). From (Fig. 1) differential thermal
analyses of the studied glasses showed endothermic peak
temperatures recorded at about 683 ◦ C while exothermic
peak recorded at about 840 ◦ C, the wide of the exothermic
(3) crystallization of the studied glass-ceramic samples.
X-ray diffraction (Table 2 and Fig. 2) indicates that diop-
side, magnetite and minor amounts of anorthite were the main
crystalline phases formed in sample 3-B1 (after heat treat-
ment at 900 ◦ C for 2h). In sample 6-B1 (thermally treated
at 1000 ◦ C for 2h) the X-ray patterns show increasing

Fig. 2 XRD of the investigated

basalt glass that are thermally
treated at 900 and 1000 ◦ C
for 2 h
Silicon (2019) 11:579–592 583

Fig. 3 SEM micrographs of the

investigated glass samples;
a sample no. 2-B1, thermally
treated at 850 ◦ C, b sample
no. 3-B1, thermally treated at
900 ◦ C, c sample no. 4-B1,
thermally treated at 950 ◦ C, and
d sample no. 6-B1, thermally
treated at 1000 ◦ C

the percentage of the diopside and magnetite phases with
decreasing of the anorthite phases.
The SEM microscopic examination of samples no.
2-B1 and 3-B1 (heat treated at 850 ◦ C and 900 ◦ C
for 2h, respectively) shows surface crystallization and
coarse grained textures. While in samples 4-B1 and 6-B1
(thermally treated at 950 ◦ C and 1000 ◦ C for 2h showed fine
crystals textures and bulk crystalline (Fig. 3).
The obtained values of the electric conductivity indicate
a range varies between 2.0 x 10−4 μs/cm at 42 Hz for
sample no. 4 and 33.34 μs/cm at 8 MHz for sample
no. 3 as shown in Table 3. It indicates a wide range of
variation with some anomalous low values recorded at the
start of sweeping measurements at 42 Hz. Sample no. 3
seems to have relatively higher conductivity (σ ) than the
other samples through the overall behaviour, whereas (σ )
seems to have the lower values for samples no. 2 and
6 as shown in Fig. 4. The obtained conductivity values
for the studied basaltic glass and glass-ceramic seem to
be much higher and out of the range of conductivity
(10−5 -10−9 μs/cm) measured by Mostafa et al. [21]
for some Egyptian basalt at different temperatures. The
studied samples are characterized by conductivity values
in the range of insulators and semiconductors (insulators
<10−8 S/cm <semiconductor <103 S/cm <conductors).
For simplicity, the studied electric behaviour (electric
signature) can be divided into three stages; 1) Initial Pre-
saturation stage (A), commonly known as DC-stage (42Hz

Table 3 Electric properties of the measured samples as a function of the electric frequency

Sample No. ε ε σ (μs/cm)

42 Hz 2.0 MHz 3.5 MHz 8.0 MHz 42 Hz 2.0 MHz 3.5 MHz 8.0 MHz 42 Hz 4.5 MHz 6.0 MHz 8.0 MHz

1 9.73 9.00 8.78 8.29 0.72 0.18 0.14 0.07 0.0011 4.42 6.85 32.18
2 9.28 8.57 8.38 7.74 0.69 0.17 0.13 0.09 0.0036 3.99 6.20 30.85
3 9.07 8.38 8.16 7.61 0.68 0.15 0.14 0.03 0.0004 5.37 8.59 33.34
4 9.16 8.51 8.37 7.95 0.69 0.22 0.17 0.04 0.0002 4.69 7.24 30.34
5 9.27 8.68 8.54 8.07 0.69 0.20 0.16 0.06 0.0013 4.61 6.61 30.55
6 9.99 9.29 9.15 8.84 0.75 0.25 0.19 0.04 0.0027 3.99 5.62 29.59

where, ε is the dielectric constant, ε is the dielectric loss and σ is the electric conductivity
584 Silicon (2019) 11:579–592

a c

Fig. 4 Electric conductivity (σ ) of the investigated glass samples as the frequency range 42-4500 kHz, b transitional stage in the frequency
a function of the electric frequency. A detailed illustration of this range 4500-6000 kHz, and c final abrupt increase in the frequency
behaviour can be divided into three stages; a pre-saturation stage in range 6000-8000 kHzW

– 4.5 MHz), 2) Transitional stage (B) (4.5-6.0 MHz), and 3) Results of the dielectric constant (ε  ) were swept at
Final stage (C) (6.0-8.0 MHz) (Fig. 4). Stages (B) and (C) different electric frequencies ranging from 42 Hz up to
(4.5-8.0 KHz) are known as AC-stage. 8MHz (Fig. 5). The range of variation seems to be limited
Silicon (2019) 11:579–592
Fig. 5 Dielectric constant (ε ) of
the investigated glass samples as
a function of electric frequency.
A detailed illustration of this
behaviour can be divided into
three stages; a initial stage in the
frequency range 42-2000 kHz,
b transitional stage in the
frequency range 2000-3500
kHz, and c final stage in the
frequency range 3500-8000 kHz
starting from 9.07 (sample 3) up to 9.99 (sample 6) at 42
Hz (Table 3). Generally, the highest (ε  ) values are recorded
for sample no. 6 and the lowest values for sample no. 3
(Fig. 5). The measured values show some steady decrease
at the lower frequencies down to 2 MHz with constant slope
(initial stage, A), then slight decrease followed by a slight
increase up to a frequency level at 3.5 MHz (transitional
stage, B). Finally, the decrease continues in its steady
decrease till reaching the end of measurement at 8 MHz,
the final stage(C) (Fig. 3). However, in general the obtained
curve decreases slightly with a steady slope and can be modeled
using a general empirical equation as shown in Table 4.
The fluctuation of the measured values is higher for
the dielectric loss (ε ) (Fig. 6) than that assigned for the
dielectric constant (ε ). The dielectric loss values also show
a relatively steep decrease through the initial stage (A)
decrease till reaching 2 MHz. The (ε  ) starts with 0.68 at
42 Hz (sample no. 3) then go to much fewer values at the
end of this stage (ε  = 0.15 at 2 MHz). The behaviour
of the ε − f curve through the transitional stage (B) is
highly fluctuated and can’t be modeled except for sample no.
6 (Table 4). A slight decrease in the ε  values can be noticed in
the final stage (C) (Fig. 6). In general, sample no. 6 shows the
highest (ε ) as the sample no. 3 shows the lowest (ε  ) values.
4 Discussion
4.1 Characterization
The differential thermal analysis (DTA) was a useful tech-
nique in determining the temperature range of crystalliza-
tion and heat-treatment range to be applied to the investi-
gated samples. The endothermic peak may show molecular
585
a
b
c
rearrangement before glass crystallization [22]. The degree
of crystallization fluctuates around ±30◦ of the crystal-
lization peaks due to the milled glass. Surface nucleation
and crystallization tend to obscure the internal structural
changes [23]. The extensive nature of the exothermic peaks
(Fig. 1) indicates the broad temperature range during crys-
tallization of the studied glass samples.
Figure 2 and Table 2 show that all samples from 2-B1
to 6-B1 are composed of diopside (CaMgSi2 O6 ), magnetite
(Fe3 O4 ) and anorthite phases. Diopside pyroxene seems
to correspond to the main crystalline phase in the wholly
crystallized samples. The elevated frequency of the diopside
sign together with the experimental small shift of the
diffraction position towards higher 2θ values in relation to
the standard ASTM d-spacing (ASTM powder file 11-654)
indicates the presence of solid solution most, perhaps of Ca-
Tschermak’s component (CaAl2 SiO6 )-diopside pyroxene.
This appears the formation of pyroxene phases in quantities
better than their normative principles. This is superior by the
tendency of aluminum to share in the building of compound
pyroxenes.
The dislocation of the main characteristics d- spacing
lines of the pyroxene range towards higher 2θ values might
support the proposal that Al3+ was induced in the pyroxene
solid solutions of diopside type. Omar and El-Shennawi [24]
studied the crystallization of basaltic rocks and basaltic-like
silicate melts and showed that the boundary curves between
the plagioclase and pyroxene fields of crystallization are
displaced towards the widening of crystallization field of
complex aluminous pyroxene phases.
Diopside is the most extensive part of pyroxenes
and represents a group of minerals which are directly
connected with the chemical formula of CaMgSi2 O6 of
equal structures, but containing dissimilar percentages of

Table 4 The final electric model for the studied samples
Item S. No. Initial stage (A)
Dielectric 1 ε = 2 x 10−8 f 2 –0.0003f + 9.20 (R2 = 0.976)
Constant (ε ) 2 ε = 2 x 10−8 f 2 –0.0004 f + 9.76 (R2 = 0.980)
3 ε = 2 x 10−8 f 2 –0.0004f + 9.04 (R2 = 0.980)
4 ε = 2 x 10−8 f 2 –0.0003f + 9.23 (R2 = 0.967)
5 ε = 2 x 10−8 f 2 –0.0003f + 9.10 (R2 = 0.969)
6 ε = 2 x 10−8 f 2 –0.0003f + 9.93 (R2 = 0.975)
Dielectric 1 ε = −4 x 10−8 f 2 -0.0001f + 0.556 (R2 = 0.993)
Loss (ε  ) 2 ε = −4 x 10−8 f 2 -0.0002f + 0.652 (R2 = 0.994)
3 ε  = −4 x 10−9 f 2 -0.0002f + 0.650 (R2 = 0.993)
4 ε  = −4 x 10−8 f 2 -0.0001f + 0.662 (R2 = 0.994)
5 ε  = −3 x 10−8 f 2 -0.0002f + 0.658 (R2 = 0.994)
6 ε  = −3 x 10−8 f 2 -0.0002f + 0.731 (R2 = 0.994)
Electric Conductivity 1 σ = 2 x 10−7 f 2 - 1.3 x 10−4 f + 0.093 (R2 = 0.981)
σ (μs/cm) 2 σ = 2 x 10−7 f 2 -2.5 x 10−4 f + 0.129 (R2 = 0.978)
3 σ = 3 x 10−7 f 2 - 4 x 10−6 f + 0.067(R2 = 0.988)
4 σ = 2 x 10−7 f 2 - 8 x 10−5 f + 0.080 (R2 = 0.985)
5 σ = 2 x 10−7 f 2 - 3 x 10−6 f + 0.029 (R2 = 0.983)
6 σ = 2 x 10−7 f 2 - 5 x 10−5 f + 0.044 (R2 = 0.973)
586
Transitional stage (B) Final stage (C)
——– ε = 5 x 10−9 f 2 - 0.0001f + 0.40 (R2 = 0.872)
——– ε = 4x 10−9 f 2 - 0.0001f + 0.39 (R2 = 0.860)
——– ε = 3x 10−9 f 2 - 0.0001f + 0.33 (R2 = 0.819)
——– ε = 5x 10−9 f 2 - 0.0001f + 0.45 (R2 = 0.795)
——– ε = 5x 10−9 f 2 - 0.0001f + 0.47 (R2 = 0.838)
ε = 6 x 10−8 f 2 + 0.0003f - 0.077 (R2 = 0.692) ε  = 4x 10−9 f 2 - 0.0001f + 0.48 (R2 = 0.874)
σ = −7 x 10−7 f 2 + 0.008 f - 20.2 (R2 = 0.812) σ = 1 x 10−7 f 2 + 0.102 f - 59.4 (R2 = 0.997)
——– σ = 2 x 10−7 f 2 + 0.0084f – 52.2 (R2 = 0.997)
σ = −1 x 10−6 f 2 + 0.017 f - 43.2 (R2 = 0.922) σ = 5 x 10−7 f 2 + 0.0045 f - 37.9 (R2 = 0.997)
σ = −8 x 10−7 f 2 + 0.0096 f - 22.7 (R2 = 0.773) σ = 5 x 10−7 f 2 + 0.0046 f – 36.8 (R2 = 0.997)
σ = −6 x 10−7 f 2 + 0.0077 f - 16.5 (R2 = 0.505) σ = −8 x 10−8 f 2 + 0.0124 f – 64.6 (R2 = 0.997)
——– σ = −9 x 10−8 f 2 + 0.030 f – 68.9 (R2 = 0.997)
Silicon (2019) 11:579–592
Silicon (2019) 11:579–592
a c
Fig. 6 Dielectric loss (ε ) of the investigated glass samples as a func-
tion of the electric frequency. A detailed description of this behaviour
can be divided into three stages; a initial abrupt decrease stage in the
sure elements [25]. In the light of the new results, it is
stated that there is an intermediary association between
diopside (CaMgSi2 O6 ) and Ca-Tschermak (CaAl2 SiO6 ).
This member represents a mineral middle between these two
minerals beside to this series, where Al3+ occupies both
587
frequency range 42-2000 kHz, b transitional steady stage in the fre-
quency range 2000-3500 kHz, and c final slight decrease stage in the
frequency range 3500-8000 kHz
octahedral (AlO6 ) and tetrahedral (AlO4 ) position in the
structure.
Figure 3 shows SEM micrographs of the crystallized
samples. From the microscopic investigations of samples
2-B1 to 6-B1, it can be observed that crystallization
588
began in samples 2-B1 and 3-B1 at relatively low
temperatures and gives up a surface crystallization. While
in samples 4-B1 and 6-B1 crystallization starts at higher
temperatures and gives up bulk crystallization. The bulk
nucleation predominates in samples 2-B1 & 6-B1, where
crystallization readily took place throughout the entire
volume of these samples and crystal sizes ranging from
120-170 nm 6-B1 (Fig. 3d) and 210-260 nm 2-B1 (Fig. 3a).
Samples 2-B1 and 3-B1 were thermally treated at rela-
tively low temperatures 850 ◦ C and 900 ◦ C, respectively;
therefore they did not give up a full surface crystallization
and still contain a high proportion of residual glass, leading
to the formation of coarse grain texture (Fig. 3a,b). While
samples 4-B1 and 6-B1 were thermally treated at higher
temperatures 950 ◦ C and 1000 ◦ C, respectively; and give up
complete bulk crystallization, which led to the formation of
fine grained texture (Fig. 3c,d) [26].
The relatively high fluctuation of the electric conductiv-
ity by increasing the frequency is referred as an electric
signature which is diagnostic for the composition of the
studied samples [27]. In their studies on the electric resis-
tivity of iron and stony meteorites, Nabawy and Rochette
[27] mentioned that the electric signature of the iron mete-
orites is much complicated than that of siliciclastic mete-
orites. Therefore, the presence of mafic minerals like iron
oxides content causes much more complicated and fluctu-
ated electric behaviour (electric signature) than the felsic
minerals-bearing rocks.
They divided the electric signatures into four main
electric stages: 1) Pre-saturation stage or “building up
energy stage”, in which the measured electric resistivity
increases up with one or more peaks. In the present
study, this stage is characterized by very high values; 2)
threshold stage or “steep stage”, in which the material
attains the saturation stage and the measured electrical
resistivity decreases steeply with increasing the frequency;
3) transitional stage; and 4) steady stage, in which
increasing the electric frequency has a slight or no effect on
the electric resistivity.
However, though they classified the electric signature
into four stages, they referred that the first peak in the first
stage mostly starts early at less than 100 Hz and that this
stage finishes early at 1 kHz, whereas they can’t access the
steady stage for the iron meteorites and Fe-Ni alloys till
the end of the measuring frequency at 100 KHz, i.e. it is
present at higher frequencies. For the present study which
starts at 42 Hz, the measured conductivity increases slightly
through the initial stage (A) which may be assigned as pre-
saturation stage (A) ended mostly at frequencies more than
4.5 MHz (Fig. 4a) with a relatively low conductivity. Then
the electric signature of the studied samples go through the
transitional stage (B) where the electric conductivity to be
steady (Fig. 4b), i.e. the steady stage of the iron-bearing
Silicon (2019) 11:579–592
materials that have not been by Nabawy and Rochette [27]
can be assigned at frequencies more than 4.5 MHz. Finally,
the studied samples cross the transitional stage (B) into the
final abrupt increase stage (C) at frequencies higher than 6
MHz where the electric conductivity increases abruptly with
much higher rate (Fig. 4c). So the present electric signature
could be considered as a complementary behaviour for that
assigned for the iron-bearing meteorites and alloys [27].
The obtained conductivity values for the studied basaltic
glass and glass-ceramic seem to be out of the range of con-
ductivity (10−5 -10−9 μs/cm) measured for some Egyptian
basalt (collected from the Eastern Desert) at different tem-
peratures [21]. The present glass-ceramic basalt samples
(collected from Sinai Peninsula) are characterized by rela-
tively higher conductivity and higher dielectric constant val-
ues. These relatively high values are mostly related to higher
percentage of mafic minerals (conductive iron oxide, FeO,
Fe2 O3 , Fe3 O4 ), where the aphanitic rocks (extrusive rocks
formed from lava crystallization with fine to very crystals,
e.g. basalt, andesite and rhyolite) with mafic constituents
causing a significant increase of conductivity by an order
of magnitude than the phaneritic rocks (intrusive igneous rocks
with relatively coarse crystals, e.g. gabbro, diorite and gran-
ite) of the mafic same composition [21, 28].
The behaviour of the dielectric constant values (ε ) as a
function of the electric frequencies (Fig. 5) seem to be simple in
correlation to the electric conductivity and the dielectric loss
(Figs. 4, 5 and 6). The (ε  ) values decrease slightly through the
initial stage (A) up to 2.0 MHz with 6.36-7.65 % decrease
in the (ε  ) values. The transitional stage (B) extends from 2
MHz up to 3.5 MHz with additional slight decrease followed
by abrupt increase in the values through this stage causing a
slight decrease (1.40-2.43 %) as a net result for this fluctu-
ation. Finally, the values continue in their slight decreasing
at the same rate causing a total slight decrease for the different
samples at the end of the measuring process (11.5-16.6%).
The simplicity of this behaviour is accompanied by some
fluctuations at the higher frequencies (>6MHz, Fig. 5).
However, the decrease of the (ε ) values at the end of the mea-
suring process is not more than 17 % for all the basaltic
glass and glass-ceramic samples.
A decrease in the (ε ) with increasing frequency is
common in most of the dielectric materials due to the
dielectric relaxation, as the speed of the dipole rotation of
most polar materials at high frequency (f ) is insufficient to
match the shift in the applied AC bias [29]. At the ambient
conditions, this dipole rotation follows the AC field. At
higher frequencies, it seems that the dipole rotation and
molecular mobility became much more difficult. In other
words, decreasing the (ε  ) with increasing frequency means
that the molecular rotation and rearrangement became more
difficult and the friction between molecules increases with
increasing (f ).
Silicon (2019) 11:579–592
On melting the basalt samples and after their thermal
treatment at different temperatures, the obtained glass-
ceramic samples contain some free metals (e.g. Fe2+ , Al3+ ,
Ca2+ , Mg2+ , Na1+ and Ti4+ ) that elaborated and enforced
at relatively higher frequencies. Comparing the dielectric
values for the different samples indicates that the higher
(ε ) is assigned for sample 6-B6 which has been thermally
treated at 1000 ◦ C. This sample has lower anorthite than
that for the other samples, i.e. higher free Al3+ ions. On
contrary, the least (ε  ) is assigned for sample 3-B3 which has
the highest anorthite i.e. lower free Al3+ ions and therefore
more systematic behaviour for the dielectric constant as a
function of frequency.
Some similar case studies on basalts, sandstones and
heterogeneous materials, in which (ε  ) decreases with
increasing frequency with some disturbance and beaks
through the measuring process, at the higher frequencies in
particular, have been published by some authors [30–34].
Ahmad and Zihlif [34] on their study on electric properties
of basalt rocks indicated similar behaviour to our present
studies in the range of 10-1000 Hz, whereas Li et al. [29]
showed similar behaviour on their studies on glass fiber
PCB substrate at frequencies more than 400 KHz.
This dielectric behaviour of the heterogeneous materials
(e.g. basaltic glass-ceramic) can be also explained by the
Maxwell-Wagner polarization mechanism. In the Maxwell–
Sillars polarization a separation of charges occurs, with
a considerable distance relative to the atomic and molec-
ular sizes. Therefore, it becomes easier for the ions to
rotate freely with increasing the frequency and the contribu-
tion to dielectric loss can therefore be orders of magnitude
larger than the dielectric response due to molecular fluc-
tuations. This polarization mechanism occurs either at the
inner dielectric boundary layers on a mesoscopic scale or at
the external electrode-sample contact interface on a larger
macroscopic scale [35]. This mechanism can be explained
in more details by describing the inhomogeneous structure
as a double or multi-layers arrangement, where each layer is
characterized by its dielectric and its conductivity proper-
ties. In addition, since conductivities of the different layers
are frequency dependent, therefore the double layer com-
posite generally has a frequency dependent relaxation time
even if the individual layers are characterized by frequency
independent dielectric properties (DC behaviour). There-
fore, the dielectric properties of the basalt samples are
the net result of a multi-layer arrangement including the
diopside, Anorthite and Magnetite phases in which the per-
centage of the Anorthite seems to be the key-factor control
for that behaviour
The dielectric loss (ε  ) decreases by decrease the
dielectric constant values and increase the applied AC
frequency with relatively high fluctuations through the final
stage (C) but with some increase in the (ε ) values at the
589
start of the measurement followed by decrease of the (ε  )
at frequencies higher than 1 kHz. The dielectric loss for the
studied samples seems to be relatively low in relation to
the dielectric constant values through the initial stage (A)
(ε /ε ≤ 7.5 %) and abruptly decreased through transitional
(B) to less than 2.7 %, whereas diminishes at the final stage
(C) to ≤ 1.15 % (Fig. 6: B, C). Therefore, thermal heating
of the glass-ceramic basalt with increasing frequencies is
accepted, at the higher frequencies in particular.
Correspondence of the behaviour of the X-Y plots of
the electric properties of the studied basalt samples as a
function of frequency indicates increasing the (σ ), and
decreasing both (ε ) and (ε ) with increasing frequency
(Figs. 4, 5 and 6). This correspondence can be attributed to
ionic polarization that created on applying the external AC
field that causes displacement of the positive and negative
ions of the mafic minerals in the glass-ceramic basalt (i.e.
increasing the polarization) up to the point where the ionic
bonding force can stop this displacement.
4.2 Modeling
Modeling process is applied to the measured electric values
after finishing the characterization of the electric properties
and ranges of the basaltic glass-ceramic samples. Prediction
of electric behaviour and values at different frequencies
is the main purpose for the modeling process. Modeling
the dielectric constant is easier than the other parameters,
where its behaviour is more consistent with increasing the
applied frequency. The obtained model equations are listed
in Table 4. The reliability of the obtained equations of
the dielectric constant (ε ) as a function of frequency (f )
for the different samples is very high (R2 ≥ 0.967), i.e.
predicting the (ε  ) seems to be typically 97% close to the
real value. Representing the obtained model as ε = a.
f 2 – b. f + c reveals that the similarity in the factors
a & b (Table 4) indicates that the slope of the ε  − f
curves is typical. The slight difference in the constant value
(C) indicates the intercept with the y-axis, i.e. refers to the
sample having the higher dielectric constant ε  . The highest
value for constant C is assigned for sample no. 6 (C = 9.93),
whereas the lowest values are assigned for sample 3 (C =
9.04, Table 4). Therefore, it is indicated that the highest
dielectric constant is assigned for the glass-ceramic sample
that has been thermally treated up to 1000 ◦ C, i.e. which has
the highest diopside content (Fig. 2). A bulk model can be
introduced tracing this relationship as follows.
ε  = 2 × 10−8 f 2 − 0.0003f + C1 (R2 ≥ 0.969)(42Hz − 8.0MHz) (4)
Where C1 is a constant referring to the mineral
composition, it increases with increasing the diopside
content.
590
Though the dielectric loss ε increase by increasing the
ε ,modeling the ε seems to be much more complicated
than that for the ε . Therefore, discriminating the dielectric
loss signature into three stages helps greatly in the modeling
process. The behaviour of ε through the transitional stage
(B) (2 -3.5 MHz) seems to be hazy and highly complicated
to be traced except for sample no.6 with the well-developed
diopside phase (Fig. 6B, Table 4). In the initial stage (A),
the steady decrease in ε values can be easily traced and
modeled in high precision (R2 = 0.994). It can be generally
represented by the following model.
ε = −4 × 10−8 f 2 − 0.0002f + C2 (R2 = 0.994) (42Hz − 2.0MHz)
(5)
Where; C2 value is related to the diopside content.
Increasing the constant C2 refers to increasing the
diopside content, so the highest value is assigned for sample
no. 6 that has the highest diopside content. C2 increases
consistently from sample no. 1 (that represents the initial
stage model where no thermal treatment) up to sample no. 6
(thermally treated at 1000 ◦ C). For sample no. 3, the effect
of the thermal treatment seems to be mixed up with the
effect of mineral composition similar to that for ε behavior
(Table 4).
The plot of the electric conductivity (σ ) as a function
of the applied frequency is less complicated than that of
ε − f plot (Fig. 6). The σ − f plot can be sliced into three
main parts; initial (A) (42Hz-4.5 MHz), transitional (B)
(4.5-6.0 MHz), and final stages (C) (6.0-8.0 MHz). In the
initial stage, the relationship between the two parameters
seems to be steady, DC stage and can be modeled with very
high precision (Table 4). A general model can be introduced
to calculateσ as a function of f in stage (A) as follows.
σ = 2×10−7 f 2 −C3 f +C4 (R2 ≥ 0.973)(42Hz−4.5MHz)
(6)
Where, both are constantly based on the diopside content
and the thermal treatment.
The lowest C3 and C4 values are assigned for samples
no. 6 (treated at 1000 ◦ C) and 5, (treated at 950 ◦ C, polished
sample) whereas the highest values are recorded for sample
no. 3 (treated at 900 ◦ C). Through the transitional stage, the
electric signature of the studied samples can be modeled for
some samples with less precision than that for the initial and
final stages (Table 4). The precision of modeling process
increases through the final stage (R2 = 0.997). However,
values of the multiplication factors and the constant of the
obtained equations vary from sample to sample, i.e. it is
not accepted to a general model for the different samples
(Table 4). This could be explained by the fact that at lower
frequencies, the electric charges and energies are relatively
low and not so enough to start the electric flow (σ ) and
Silicon (2019) 11:579–592
therefore the polarization (ε  ) is relatively high, whereas at
higher frequencies the electron flow (σ ) and electric charges
are higher and therefore the ability of electrons to rotate as
fast as changing the frequency (changing the positive and
negative electrodes) and the polarization (ε  ) decreases. This
behaviour should go through a transitional stage.
4.3 Applications as Insulators and Semiconductors
For a given material to be considered as insulator, it
should be poor electric conductor (insulators <10−8
S/cm <semiconductor <103 S/cm <conductors). For the
insulating material, it should be consists of electronic
bands, some of them are completely filled with electrons
and in between there are completely empty bands, i.e.
empty band is surrounded by higher filled band valence
and next higher conduction band (filled with electrons).
This band gap between both the conduction and valence
bands are large enough for insulation and for preventing
the electrons from transfer between the different bands,
i.e. high energy is needed to promote electrons into the
conduction band. This energy can’t be obtained at the room
temperature and heating is needed. A dielectric material is
an insulating material for electric current flow. It exhibits
an electric dipole structure, where the negative and positive
charges displace their positions, i.e. their center of gravity
is different. They can be polarized on applying the electric
field [36].
The dielectric polarization causes positive charges to
be displaced toward the applied electric field and the
negative charges to be shifted in the opposite direction.
The dielectric insulator can be considered as a polarized
material (charges accumulated on its surface) with no
internal charges (average charge inside the dielectric is zero)
[37].
All dielectrics are electrical insulators. However, at the
room temperature, the dielectric insulators can conduct a
few amounts of electricity but along their most surface
and impurity ions [38]. Though the electric conductivity
values seem to be close to each other for the different
samples in the initial stage, at frequency less than 1 MHz in
particular, curves separation is noticed at frequencies higher
than 5 MHz with higher electric charges. The least values
are assigned for sample no. 6 (treated at 1000 ◦ C) with
higher diopside content. The higher conductivity values
are recorded for samples no. 1 (basaltic glass) and no. 3
(treated at 900 ◦ C). The highest dielectric constant values
are assigned for sample no. 6, whereas the lowest values are
assigned for sample no. 3, i.e. the polarization and insulation
is the highest for sample no. 6. Therefore, the thermal
treatment for the studied samples up to 1000 ◦ C helped
in enhancing the dielectric properties and insulation of the
basaltic glass-ceramic by increasing the diopside content.
Silicon (2019) 11:579–592
On applying the electric field and due to the polarization
process and insulation for the current flow some energy
is lost in the form of thermal radiation represented by the
dielectric loss which seems to be relatively low for the
studied samples. Percentages of the dielectric loss to the
dielectric resistivity fluctuates around 7.5% at 42 Hz and
decreases to less than 2% at 3.5 MHz and less than 1% at
8.0 MHz. Therefore, thermal radiation and loss in charges at
the different frequencies, at higher frequencies in particular,
through the basaltic glass-ceramic are accepted.
5 Conclusions
Based on the electric conductivity and the dielectric
properties of the studied basaltic glass-ceramic, it is
accepted as insulating material for different applications.
The thermal treatment up to 1000 ◦ C helped in enhancing
the insulating dielectric properties of the studied samples
with the highest dielectric properties and the lowest electric
conductivity assigned for the basaltic glass-ceramic that
treated to this high temperature. However, a slight difference
could be noticed between the electric conductivity values
for the different samples. This thermal treatment increased
the diopside content and decreased the anorthite content.
Due to high energy accompanying the applied electric
current at high frequencies up to 8 MHz, some vigorous
behaviour and anomalies are recorded at this high level of
frequency.
Acknowledgments This work was done within the framework of the
research project No. 10060401 entitled “Utilization of Sinai Basaltic
Rocks for the Production of Construction Materials” sponsored by
National Research Centre. The authors would like also to thank the
reviewers and the Editor for their constructive comments that greatly
enhanced the manuscript.
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