CHAPTER NO 2

LITERATURE REVIEW
2.1 OBJECTIVE OF THE PROJECT
Aim of this project was synthesis and characterization of paraffin based, nanomagnetite composite (PNMC) and thereby increasing the thermal conductivity of
paraffin.
2.2 PROJECT DETAILS
Paraffin is a common organic phase change material (PCM) with many applications in
thermal energy storage (TES) systems.[1] To improve the thermal conductivity of this
paraffin, we reinforced the paraffin with nano-magnetites by using dispersion
technique. The nano-magnetites were synthesized in laboratory by using the cost
effective sol gel technique. The PNMC thus formed was studied and characterized by
using various techniques and study methods.
2.3 PHASE CHANGE MATERIALS
Substances that can absorb and release thermal energy during the process of melting
and freezing are called as phase change material (PCM). In the form of latent heat
PCM releases a large amount of energy at constant temperature. Similarly, during
melting PCM absorbs large amount of heat. Recharging behavior of PCM at ambient
temperature fluctuations makes it ideal for application which requires temperature
control.
PCM can be used over broad range of temperature -40c to 150c. heat storage per
unit volume of pcm is 4 to 15 time more than masonry, rocks and water. [2]
2.3.1 APPLICATIONS OF PCM
As a result of increasing demand for energy saving, eco-friendly materials in
building/construction, industries and refrigeration, Thermal energy storage (TES),
electronics and textile, PCM market is experiencing a higher growth in the past few
years. Application of PCM includes:

Refrigerators and freezers that use less energy.

High-performance textiles that provide relief from hot and cold conditions.
PCM are also used in shipping containers to keep the goods at required
temperature for longer periods.
Construction material that keeps living spaces comfortable and reduces
heating and cooling costs.
TES systems that shift a buildings cooling and heating needs to cheaper.

2.3.2 COMMONLY USED PCM

1

Paraffin (CnH2n+2) and fatty acids (CH3(CH2)2nCOOH)

Water-based ice and gel packs

Salt hydrates (MnH2O)

2.4 PARAFFIN
Paraffin wax is a white or color less soft solid derivable from petroleum, coal or
oil shale. Paraffin contains twenty to forty carbon atoms. At room temperature
paraffin is solid and only begins to melt above approximately 37 C (99 F ); [3] its
boiling point is >370 C (698 F).[4].

Fig. 2.1 paraffin pellets.

2.4.1 PROPERTIES
Paraffin wax is a white, tasteless, odorlessm waxy solid, with a typical melting
point between about 46 and 68 C. Fig 2.1 [8] The density of paraffin is around 900
kg/m3. [9] Paraffin is unaffected by most common chemical reagents but burns
readily. Its heat of combustion is 42 kJ/g.
Paraffin wax has an specific heat capacity of 2.142.9 J g 1 K1 and a heat of
fusion of 200220 J g1.[12] This property is subjugated in improved drywall for
home building material: a certain type of wax (with the right melting point) is
filled in the drywall during manufacture so that it melts during the day, absorbing
heat, and solidifies again releasing the heat at night.[13] Wax expands considerably
when it melts and therefore its used in wax thermostatic element thermostats for
industrial, domestic and, particularly, automobile purposes.[15][16]
During melting paraffin emits fumes which may cause irritation in lungs, nose,
throat and eyes. So face mask and safety googles are necessary when melting
paraffin. For those with sensitive skin, melted wax can cause thermal burns.
Therefore, proper clothing and safety gloves should be used when handling melted
wax.

2.4.2 APPLICATIONS OF PARAFFIN

Paraffin is used in candle making

Coating for waxed paper or cloth

Investment casting

Neuron radiation shielding

Phase change material for thermal energy storage, etc.

2.5 NANO-MAGNETITE
Nano-magnetite are iron oxide particles with diameters between about 1 and
100 nanometers. Due to their super paramagnetic properties, magnetite have wide
range of applications in many field. Therefore have attracted a lot of interests.

Fig. 2.2 structure and unit cell of magnetite.

2.5.1 PROPERTIES OF MAGNETITE

2.5.1.1PHYSICAL PROPERTIES
Micro-scale crystals of natural and synthesized magnetite exhibit metallic luster and
opaque jet black color. Magnetites density is established at 5.18 g/cm 3, pure iron (Fe) has a density of 7.87 g/cm3. Identical to glass at ambient temperatures, the
hardness is 5.5 of magnetite particles. [17]
According to synthesis method, effective surface areas of magnetite may vary.

As certain procedures generate coarser/finerparticles; however, typical micro-scale

particles with approximate diameters of 0.2 m exhibit surface areas of approximately
6 m2g-1[18] Magnetite particles are not porous. [17]
Standard Gibbs free energy of magnetite formation is around -1012.6 kJ/mol;
therefore, formation of magnetite is thermodynamically favorable. [17]
Additionally, the standard enthalpy and entropy of magnetite formation are -1115.7
kJ/mol and 146.1 kJ/mol/K, respectively.[19]

2.5.1.2 THERMAL PROPERTIES

Magnetite melting/boiling points are observed at 1590C and 2623 C, respectively.
Heats of fusion, decomposition, and vaporization are 138.16, 605.0, and 298.0 kJ/mol
(at 2623 C) respectively.[21]
2.5.1.3 ELECTRICAL PROPERTIES
As mentioned earlier, octahedral sites in the magnetite structure contain ferrous and
ferric species. The coordinated electrons with these iron species are thermally
delocalized and travel within the magnetite structure causing high conductivity
exchange constants: ranging from -28 JK to 3 JK between octahedral/tetrahedral
sites and octahedral/tetrahedral sites, respectively [22]
.

2.5.1.4 MAGNETIC PROPERTIES

Magnetites Curie temperature is observed at 850 K. Therefore, at room temperature,
magnetite is ferrimagnetic. As temperatures raised to the Curie temperature, During
thermal fluctuations, ferromagnetic alignment of magnetic moments on tetrahedral
sites gets destroyed; hence, ferromagnetic strength is diminished. When the Curie
temperature is achieved, net magnetization becomes zero and super paramagnetic
behavior is observed.

2.6 Thermal Conductivity Case Study

Paraffin is a common phase-change-material (PCM) subjugated to many thermal and
solar energy storage applications. In this study, the effect of adding nano-materials to
enhance paraffin's thermal performance is explored. Nanomagnetite (Fe3O4) particles
were prepared by solgel method for this investigation
Nano-magnetite (Fe3O4) was synthesized from Fe+2and Fe+3salt hydrates using the sol
gel method. And were stabilized by oleic acid fig 2.3.

Fig .2.3 stabilized Fe3O4.

The sizes and morphologies of nanoparticles before and after stabilization were
analyzed under a Scanning Electron MicroscopeSEM. Shown in fig 2.4,
respectively.
(a)

(b)

Fig.2.5 shows the nano magnetite (a) before and (b) after stabilization.
The thermal properties of paraffin and nanocomposite (i.e. melting and freezing point
ranges and latent heats) were measured by Differential Scanning Calorimeter. Fig 2.5.
[34]

Fig.2.6 DSC curves of Paraffin and PNMCs.

2.7CHEMICAL HAZARDS AND SAFETY PRECAUTIONS

HCL -We used HCL in our final year project for two purposes, firstly to break salt of
iron such as ferric chloride and ferrous chloride into its ions and in the second stage
we use HCL in stabilization process to maintain pH of our solution in acid way such
as 7. Working with HCL is never easy, fumes and spills can be extremely dangerous.
Therefore, proper use of googles and safety gloves is essential.

AMMONIUM HYDROXIDE (NH4OH)

Ammonia solution also known as ammonium hydroxide, is a solution of ammonia in
water. We used NH4OH in our project to obtain black precipitates while synthesizing
magnetite particles. Handling Ammonium hydroxide is difficult as it has a strong
pungent smell, Inhaling too much Ammonium hydroxide can cause nausea, headache
and dizziness. Therefore, it is advisable to use face mask and a proper ventilated fume
hoods.
FERROUS CHLORIDE (FeCl2)- A paramagnetic solid with relatively high melting
point, and is typically obtained as an off-white solid. FeCl2 crystallizes from water as

the greenish tetrahydrate. It is also soluble in water; FeCl 2 aqueous solutions are
highly transparent and pale green in color. Working with FeCl 2 dont propose such
serious hazards but, one should use proper PPEs when working.

FERRIC CHLORIDE (FeCl3.6H2O) -Ferric chloride is a hexa hydrate black-brown or

orange colored hygroscopic salt.It is non-carcinogenic and prepared by different
chemical reactions. Its chemical formula is FeCl3.6H2O.We use this chemical to
prepare nanomagnetite particles as Fe+2 of ferrous cloride and Fe+3 of ferric chloride
combine to form nanomagnetite (Fe3O4) partricles. Similar to FeCl2it doesnt cause
any immediate danger to the user. But , Proper safety measures should be taken.
OLEIC ACID -Oleic acid is brownish yellow odorless and colorless oil. The term
"oleic" is derived from, oil of olive, the oil that is predominantly composed of oleic
acid.It has chemical formula C18H34O2 . It is also known as Omega-9.It is noncarcinogenic and used in our project to avoid conglomeration of nanoparticles with
each other so it becomes stabilized. Proper use of PPEs should be carried out to avoid
any possible hazards.