ISSN: 2320-5407 Int. J. Adv. Res.

10(12), 1203-1209

Journal Homepage: -www.journalijar.com

Article DOI:10.21474/IJAR01/15958
DOI URL: http://dx.doi.org/10.21474/IJAR01/15958

RESEARCH ARTICLE
RELATIVE STUDY OF COMPRESSION RATIO VARIATION WITH PRESSURE FOR
NANOMATERIALS USING EOS

Dr. Rajendra K. Mishra1, Dr. Om Prakash Gupta2, Dr. Sudhir Trivedi3 and Dr. Prakash Dubey4
1. Department of Physics, D.B.S. College Govind Nagar, CSJM University Kanpur, Uttar Pradesh, India.
2. Department of Physics, D.B.S. College Govind Nagar, CSJM University Kanpur, Uttar Pradesh, India.
3. Department of Physics, D.B.S. College Govind Nagar, CSJM University Kanpur, Uttar Pradesh, India.
4. Department of Physics, Janata College BakewarEtawah, CSJM University Kanpur, Uttar Pradesh, India.
……………………………………………………………………………………………………....
Manuscript Info Abstract
……………………. ………………………………………………………………
Manuscript History A basic thermodynamical study of various nanomaterials has been
Received: 30 October 2022 done. Different Equation of states [EOS] (Tait, Shanker & Suzuki)
Final Accepted: 30 November 2022 have been applied and compared with the experimental result. An
Published: December 2022 derived equation using thermodynamical approximation is used to
investigate the isothermal compression and pressure dependency of
Key words:-
Nanomaterials, Volume Compression, bulk modulus of nanomaterials i.e. TiO2(rutile phase), MgO, CuO, 3C-
Bulk Modulus, Equationof State, High SiC, Zr0.1Ti0.9O2, -Fe, Rb3C60, Ge(13 nm).The acquired results are
Pressure found to be in excellent accord with known experimental data,
demonstrating the validity of the formulation utilized in this work.

Copy Right, IJAR, 2022,. All rights reserved.

……………………………………………………………………………………………………....
Introduction:-
Nanomaterials are projected to represent the tipping point in the next technological revolution in solid-state
electronics, emerging as novel structural materials, serving as medication delivery systems, and having a significant
influence across virtually all fields of research. External elements like as pressure and temperature are extremely
sensitive to nanoparticles. The study of nanoparticles under high pressure is being examined as a way to broaden the
spectrum of solid-state materials accessible. High pressure applications offer the potential to explore an infinite
number of avenues for nano-assembling or phase change in a regulated manner, and they represent a one-of-a-kind
route for the development of novel materials. Pressure application, similar to that used on bulk materials, allows for
continual alteration of the nano-interatomic object's interactions and is a useful tool for studying physico-chemical
interactions at the nanoscale and their relationship to physical attributes of interest.

The structure and interatomic spacing of materials have a substantial impact on their physical characteristics. High
pressure can change these distances, allowing us to investigate correlations between material structure and
attributes[1].

Many mechanical characteristics, such as hardness, elastic modulus, fracture, toughness, scratch resistance, and
fatigue strength, are changed and varied at the nanoscale compared to their bulk counterparts. Many nanomaterial
systems have been found to have high value of hardness. Recently, it was discovered that nano semiconductors with
decreased dimensions have electrical and optical characteristics that change with particle size, making them
attractive candidates for applications requiring tenability of optical and/or electronic properties [2].

Corresponding Author:- Dr. Rajendra K. Mishra

Address:- Department of Physics, D.B.S. College Govind Nagar, CSJM University Kanpur, 1203
Uttar Pradesh, India.
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At ambient temperature, XRD examinations of baddeleyite structures under high-pressure (20–30 GPa) behaviors of
nanocrystalline rutile TiO2 was studied and found excellent results[3].

Investigation of the compressibility in MgO with particle size 100 nm has been extensively researched since it is a
well-known refractory oxide with a wide range of industrial uses, including the production of high-temperature
rebrick, insulating materials, and so on. It has a basic rock salt structure and is a known substantial constituent of the
Earth's mantle, making it geo-physically significant. The elastic characteristics of MgO have been evaluated by a
series of static, ultrasonic, and shock compression studies[4]. Some researchers have analysed the high-energy
synchrotron radiation and Raman spectroscopy of copper oxide (CuO) at 24 nm[5]. SiC has sparked a lot of
attention since it is a highly hard and robust ceramic with applications in things like automotive brakes and clutches,
as well as ceramic plates in bulletproof vests. This material has remarkable thermal shock resistance due to its strong
thermal conductivity, minimal thermal expansion, and high strength. SiC ceramics with few or no grain boundary
imperfections retain strength at extremely high temperatures with minimal loss of strength [6].

Compression behavior and mechanical properties such as stress and strain of Zr doped nano anatase were studied.
This study investigated that the bulk modulus of anatase increases as the crystallite size decreases [7].

The synchrotron x-ray diffraction on nanocrystalline  and -Fe was performed through a diamond-anvil cell to
pressures of 46 GPa. There was no significant grain growth when they were put under pressure. Using XRD
characterized images, they have discovered that the one phase lasted at 46 GPa, which was the highest pressure in
this investigation. At the lowest pressure i.e. 7.6 GPa, through the in situ method it has been observed that -Fe did
not transition back to the phase upon decompression. However, transmission electron microscopy (TEM) images
revealed that no -Fe exist at 0 GPa. These images also revealed that via compression the crystallite size did not
change appreciably.

Research was conducted for the Rb3C60 and other nanomaterials, which utilized different equation of state (Tait,
shanker &suzuki) models for the high-pressure compression behavior study [8].

X-ray diffraction and synchrotron radiation techniques were used to investigate the equation of state and the I–II
transition of nanocrystalline Ge with crystallite sizes of 13, 49, and 100 nm. Whereas, with the reduction of the
nanomaterial particle size, the percentage volume collapse during the transition, and the bulk modulus and transition
pressure rise. However, the enhanced bulk modulus is due to compression forces induced by the amorphous grain
boundary zones in the nanophase material[9].

In this article, we present a simple theoretical approach to study the compression behaviour of nano systems under
pressure. An EOS has been developed and after examining its validity, it has been used to calculate the change in
volume of some nanomaterials under high pressure. Moreover, the results calculated from our EOS have been
compared with those obtained through other methods.

Method:-
According to property of Solid, material contract while cooling and expands on heating for a particular temperature.
It was determined by thermal expansion coefficient which is generally a function of volume and temperature at
constant pressure. And it is known as:
1 𝜕𝑉
𝛼 = 𝑉 𝜕𝑇 (1)
𝑃

Where V is volume, P is pressure and T is temperature

Utilizing simulations of single-walled Carbon nanotubes in molecular dynamics, the thermal expansion coefficient
was calculated [10] . During such study [10] used the temperature dependence of ∝ as given below;
∝ = a + b T + c T2 (2)

Where a, b, c are constants. It should be noted that the aforementioned equation does not match the initial boundary
conditions ,∝ = ∝0 𝑎𝑡𝑇 = 𝑇0 , In order to satisfy this condition eq. (2)can be write as follows
∝ = a + b (T-T0) + c (T-T0) 2 (3)
or

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1
𝛼 = 𝛼0 + 𝛼0′ 𝑇 − 𝑇0 + (2)𝛼0′′ 𝑇 − 𝑇0 2 (4)
′ ′′
Where ∝0 , 𝛼0 and 𝛼0 are the zero, first and second order derivatives of 𝛼 with temperature at 𝑇0 .
The Anderson -Gruneisen parameter 𝛿𝑇 which plays an important role in understanding the harmonic properties of
ionic solid is defined as [11]
1 𝜕𝐵
𝛿𝑇 =- ∝𝐵 𝜕𝑇𝑇 (5)
𝑇 𝑃

Where ∝ and 𝐵𝑇 are the volume thermal expansion and bulk modulus, respectively,
Using thermodynamical approximation [12]:
𝛼𝐵𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (6)
We have [13]
1 𝜕∝
𝛿𝑇 = ∝2 𝜕𝑇 (7)
𝑃
From this relationship , we will get results as follows:[14]
𝜕∝
∝′0 = 𝜕𝑇 = 𝛿𝑇 𝛼0 2 (8)
𝑃
𝜕 2∝
∝′′0 = = 2𝛿𝑇2 𝛼0 3 (9)
𝜕𝑇 2 𝑃
In which we additionally use the assumption that 𝛿𝑇 is independent of temperature (T).
𝛼 = 𝛼0 + 𝛼02 𝛿𝑇 𝑇 − 𝑇0 + 𝛼03 𝛿𝑇2 𝑇 − 𝑇0 2 (10)
Eq. (10) has shown that 𝛼 depends on 𝑇 quadratically. Moreover, considering the temperature dependence of 𝛼
given by Eq. (10) neglects the higher order terms, which may introduce the error on temperature dependence of 𝛼,
therefore, it is necessary to consider the complete from which we write as follows:
𝛼 = 𝛼0 + 𝛼02 𝛿𝑇 𝑇 − 𝑇0 + 𝛼03 𝛿𝑇2 𝑇 − 𝑇0 2 + ⋯ … … … … … ∞
Or
𝛼 = 𝛼0 1 − 𝛼0 𝛿𝑇 𝑇 − 𝑇0 −1
𝛼 −1
= 1 − 𝛼0 𝛿𝑇 𝑇 − 𝑇0 (11)
𝛼0
By taking the value of  from equation (11) and replacing it in the equation (1) gives a new equation which was then
integrated to derive the standard equation of our study as given below:
𝑑𝑉
= 𝛼0 1 − 𝛼0 𝛿𝑇 𝑇 − 𝑇0 −1 𝑑𝑇 (12)
𝑉
And boundary conditions for the initial stage are denoted as follows:
At T = 𝑇0 V = 𝑉0
Solving equation (12) with the above boundary condition results in the following form:
1
𝑉 −
log 𝑉 = log 1 − 𝛼0 𝛿𝑇 𝑇 − 𝑇0 𝛿𝑇 (13)
0
1
𝑉 −
= 1 − 𝛼0 𝛿𝑇 𝑇 − 𝑇0 𝛿𝑇 (14)
𝑉0
Where 𝑉0 and 𝛼0 are the reference values of volume expansion and coefficient of thermal expansion, respectively.
Thermal pressure (𝑃𝑇ℎ ) which is relative pressure variation of a solid or a fluid as a result to a temperature
variation at constant volume. This is taken from the literature as mentioned below[14]:
𝑇
𝑃𝑇ℎ = 𝑇 𝛼𝐵𝑑𝑇 (15)
0
In accordance with quasi-harmonic approximation [14, 15]:
𝑃𝑇ℎ = 𝛼0 𝐵0 𝑇 − 𝑇0 (16)
Where 𝛼0 is the coefficient of thermal expansion at temperature 𝑇0 &𝑇0 is the reference temperature &𝑇 is elevated
temperature in kelvin.Taking 𝑇 − 𝑇0 value from equation (16) placing into equation (14) becomes equation (17):
1
𝑉 𝛿𝑇 −
𝛿𝑇
= 1 − 𝐵 𝑃𝑇ℎ (17)
𝑉0 0
𝐵 𝑉 −𝛿 𝑇
𝑃𝑇ℎ = 𝛿 0 1 − (18)
𝑇 𝑉0
If applied pressure is 𝑃 then total pressure including thermal pressure and applied pressure can be rewritten as given
in the below terms:
𝐵 𝑉 −𝛿 𝑇
𝑃𝑇ℎ − 𝑃 = 𝛿 0 1 − 𝑉0
(19)
𝑇
Considering 𝑃𝑇ℎ = 0 as given in literature[14] equation (19) becomes:

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𝐵 𝑉 −𝛿 𝑇
𝑃 = − 𝛿0 1 − (20)
𝑇 𝑉0
However, the approximation 𝛿𝑇 equal to 𝐵0′ as discussed by Anderson[14].Where, 𝐵0′ is the first order pressure
derivation of 𝐵. Eq. (20) takes the following from:
′
𝐵 𝑉 −𝐵0
𝑃 = − 𝐵0′ 1 − (21)
0 𝑉0
1
− ′
𝑉 𝐵0′ 𝐵
Or 𝑉 = 1 + 𝐵 𝑃 0
(22)
0 0
𝑉 1 𝐵0′
Or = exp − 𝐵 ′ ln 1 + 𝑃 (23)
𝑉0 0 𝐵0
Thus, we get Eq. (23), which is same as given by Murnaghan in a different way.
As our result has been shown in comparison with these standard EOS given in literature [16][17][18] in the
following form:
Tait EOS reads as [16]
/
𝑉 1 𝑃 𝐵0 +1
= 1− / 𝑙𝑛 1 + (24)
𝑉0 𝐵0 +1 𝐵0

Shanker EOS reads as [17]

1
𝐵 ′0 +1 2
1− 1+2 𝑃
𝐵0
𝑉
= 1+ (25)
𝑉0 𝐵0′ +1
Suzuki EOS reads as [18]
1
𝐵 ′0 −1 2
1− 1+2 𝑃
𝐵0
𝑉
= 1+ (26)
𝑉0 𝐵0′ −1

Result and Discussion:-

The current approach for analyzing the effect of pressure on Nanomaterials is based on the quasi-harmonic
approximation that the product of the thermal expansion coefficient ∝and Bulk modulus 𝐵𝑇 remains constant under
pressure [15]. Using the same approximation, in this study we have investigated the effect of change of pressure on
different nanomaterials such that TiO2(rutile phase), MgO, CuO, 3C-SiC, Zr0.1Ti0.9O2, -Fe, Rb3C60, Ge(13 nm).
From the equation (22), the volume ratio (V/V0) at different pressure have been calculated. Input parameters B0& B0/
as listed in Table 1 was taken from literature. The results obtained are shown in Figures. 1-2. Similarly, with the
same input parameters, volume ratio (V/V0) have been calculated using equation (24) also known as Tait equation
and equation (25) called Shanker equation and equation (26) Suzuki EOS . Experimental data as referenced in the
figures (1-2) was taken from the various literature and compared with the result obtained by our derived equation
and different EOS. We found that there is very good agreement between theory and experiment.

On the basis of the above, it should be noted that the current method is capable of properly describing the
compressional and elastic characteristics of nanomaterials under high pressure. This may be of current interest to
researchers studying the elastic characteristics of nanomaterials under high pressure because of its simplicity and
applicability.

Table 1:- Input parameters utilized in this research.

Materials B0 B0¢ Ref.
TiO2(Rutile phase) 211 8 [19]
MgO 179 1.5 [20]
CuO 81 4 [5]
3C-SiC 245 2.9 [6]
Zr0.1Ti0.9O2 213 17.9 [7]
ε-Fe 179 3.6 [21]
Rb3 C60 17.35 3.9 [5]
Ge(13nm) 92 4 [9]

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Fig. 1:- Compression Behaviour of TiO2(Rutile Phase) Fig. 2:- Compression Behaviour of MgO
with Exp. from Ref.[22] with Exp. from Ref.[20]

Fig. 3:- Compression Behaviour of CuO with

Fig. 4:- Compression Behaviour of 3C-SiC
Exp. from Ref.[23]with Exp. from Ref.[24]

Fig. 5:- Compression Behaviour of Zr 0.1 Ti0.9O2 Fig. 6 :- Compression Behaviour of 𝝐 − 𝑭𝒆

with Exp. from Ref.[25] with Exp. from Ref.[26]

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Fig. 7:- Compression Behaviour of 𝑹𝒃𝟑 𝑪𝟔𝟎 Fig. 8:- Compression Behaviour of Ge (13nm)with Exp. from
Ref.[27]with Exp. from Ref.[28]

Conclusions:-
The current formulation may be particularly useful for analyzing the high-pressure compression behavior of solids,
especially nanomaterials, since it offers findings that are pretty near to the experimental data for nanomaterials.
However, the main benefit of this formulation is that it follows the basic thermodynamic laws at high pressure,
allowing extrapolation into realms where experimental data is not accessible.

As a result, the current formulation might be useful in designing future high-pressure tests on nanomaterial
compression behavior.

Acknowledgement:-
Authors are grateful to the Editor-in-Chief of the International Journal of Advanced Research for a critical reading
of the manuscript and his valuable comments.

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