CHAPTER 2

2.0 LITERATURE REVIEW

2.1 CONVENTIONAL FLUID REFRIGERANTS:

Fluid Refrigerants are used in heat pumps and refrigeration cycles. Most cycles undergo phase

transitions from a liquid to a gas and back again.

2.1.1 Background history

Early mechanical refrigeration systems used sulfur dioxide, methyl chloride and ammonia. These

compounds were found to be toxic, and so they rapidly disappeared from the market with the

introduction of Chlorofluorocarbons (CFCs) (D. Sendil Kumar, 2013). Occasionally, one may

encounter older machines with methyl formate, chloromethane, or dichloromethane (called

Carrene in the trade).

Chlorofluorocarbons were little used for refrigeration until better synthesis methods were

developed in the 1950s which reduced their cost. Their domination of the market was called into

question in the 1980s by concerns about depletion of the ozone layer (D. Sendil Kumar, 2013).

2.1.2 Environmental Impacts:

Green House gas (GHG) emissions of halogenated refrigerants from vapour compression based

refrigeration, air conditioning and heat pump systems contribute significantly to global warming.
A reduction in GHG emissions can only be achieved by using environment friendly and energy

efficient refrigerants.

Fluorocarbons especially chlorofluorocarbons, became commonplace in the 20th century, their

inert nature made them preferred choices among refrigerants for many years because of their

non-flammability and nontoxicity. However, their stability in the atmosphere and their

corresponding global warming potential and ozone depletion potential raised concerns about

their usage as they were found to have numerous Ozone depletion effects (Siegfried Haaf,

Helmut Henrici, 2002). A reduction in GHG emissions can only be achieved by using

environment friendly and energy efficient refrigerants. The high environmental impacts due to

halogenated refrigerant emissions lead to the identifying of a long-term alternative to meet all the

system requirements including system performance, refrigerantlubricant interaction, energy efficiency,

safety and service (D. Sendil Kumar, 2013). These environmental impacts led to their replacement

with HFCs and PFCs, especially HFC-134a, which are not-ozone depleting, and have lesser global warming

potentials. While the HFC refrigerants have zero ozone depletion potential (ODP) they are potent

greenhouse gases. Although their total contribution to anthropogenic global warming is currently small,

these refrigerants still have global warming potentials thousands of times greater than CO 2. (D. Sendil

Kumar, 2013). The currently available refrigerants with low Global warming potential values (GWP) have

drawbacks that limit their use in many applications, such as flammability (e.g., propane), operation at

very high (CO2) or very low (H2O) pressures, or toxicity (e.g. ammonia).

In order from the highest to the lowest potential of ozone depletion are:

Bromochlorofluorocarbon, CFC then HCFC (D. Sendil Kumar, 2013).

2.1.3 Ozone Layer Depletion

The first major environmental impact that struck the refrigeration based industries is Ozone

Depletion Potential (ODP) due to manmade chemicals into the atmosphere. About 90% of the

ozone exists in the stratosphere between 10 and 50 km above the earth surface.

Molena and Rowland (1974) give in detail that chlorine based refrigerants are stable enough to

reach the stratosphere, where the chlorine atoms act as catalyst to destroy the stratospheric ozone

layer which protects the earth surface from direct ultra violet rays.

2.1.4 Global Warming Potential (GWP)

The second major environmental impact is GWP, which is due to the absorption of infrared

emissions from the earth, causing an increase in global earth surface temperature. While solar

radiation at 5800 K and 1360 W/m2 arrives the earth , more than 30% is reflected back into space

and most of the remaining radiation passes through the atmosphere and reaches the ground 1. This

solar radiation heats up the earth, which is approximately as a black body radiating energy with a

spectral peak in the infrared wavelength range. This infrared radiation cannot pass through the

atmosphere because of absorption by GHG including the halogenated refrigerants (D. Sendil

Kumar, 2013).

2.2 Refrigerant Designation "R-"Number

The designation and safety classification of primary refrigerants is according to American

Society of Heating, Refrigerating and Air-Conditioning Engineers (ASHRAE) Standard 34.

ASHRAE assigns an R-number to chemical refrigerants which are determined systematically as

follows:

Refrigerants composed of pure fluorocarbons (FC) are identified by the alpha character "R-"

followed by the corresponding HFC-number. The HFC-number describes the number of fluorine

atoms, hydrogen atoms, and carbon atoms in the molecular formula. The rightmost value

represents the number of fluorine atoms, to the left is the number of hydrogen atoms plus 1, and

two places to the left is the number of carbon atoms less one. (E.g. R-134 represents

Tetrafluoroethane CHF2-CHF2)

FC refrigerants include other haloalkane compounds such as chlorofluorocarbon (CFC), which is

a chlorinated fluorocarbon; hydrofluorocarbon (HFC), a hydrogenated fluorocarbon; and

hydrochlorofluorocarbon (HCFC), which is a CFC substitute that is more environmentally

friendly, since not all of the hydrogen has been replaced by chlorine or fluorine atoms.

2.3 NANOFLUIDS

2.3.1 Historical overview

It is a well-known fact that conventional fluids such as water, ethylene glycol (EG) and engine

oils have low thermal conductivity and the efficiency of heat transfer with a very small

temperature difference is limited. Therefore there is need for energy efficient working fluids to

improve the energy conversion system. However the coefficient of convective heat transfer

depends on thermal conductivity of the fluid. The thermal conductivity of fluid is improved by

adding micrometer or millimeter sized solid materials to the base fluids. The solid additives

improve the thermal conductivity of the base fluid. In practical, their applications are limited due
to the clogging of flow channels, sedimentation of large particles and causing pressure drops.

The above drawbacks are overwhelmed by using a new class of fluids called Nanofluids (D.

Sendil Kumar, 2013).

Nanofluids are engineered colloids which consist of a base fluid with Nano sized particles (1-100

nm) suspended within them. Common base fluids include water, organic liquids (e.g. ethylene,

tri-ethylene-glycols, refrigerants, etc.), oils and lubricants, bio-fluids, polymeric solutions and

other common liquids. Materials commonly used as nanoparticles include chemically stable

metals (e.g., gold, copper), metal oxides (alumina, silica,), oxide ceramics (e.g. Al2O3, CuO),

metal carbides (e.g. SiC), metal nitrides (e.g. AIN, SiN), carbon in various forms (e.g., diamond,

graphite, carbon nano tubes, fullerene) and functionalized nanoparticles (D. Sendil Kumar, 2013).

By suspending nanoparticles in conventional heat transfer fluids, the heat transfer performance

of the fluids can be significantly improved. As a fluid class, Nanofluids have a unique feature

which is quite different from those of conventional solid-liquid mixtures in which millimetre

and/or micrometre-sized particles are added. Such particles settle rapidly, clog flow channels,

erode pipelines and cause severe pressure drops. All these shortcomings limit the application of

conventional solid-liquid mixtures to micro channels while nanofluids instead can be used in

micro-scale heat transfer. Heat transfer performance of the nanofluid is far superior to that of the

original pure fluid because the suspended ultrafine particles remarkably increase the thermal

conductivity of the mixture and improve its capability of energy exchange (D. Sendil Kumar,

2013).

2.3.2 Techniques used in synthesis of Nano fluids

Several researches have been carried out on the synthesis of nanofluids using two step and single

step method.
In two step method, the nanoparticles are initially produced and then added to the working fluid

while in the single step method, the dispersion of nanoparticle is done directly into the working

fluid.

Synthesis of Nano fluids using two step method: The preparation of nanofluids is done by

mixing the nanoparticles directly into the base fluid. The nanoparticles are produced at first step

and then it is added into the base fluid as a second step.

Xuan and Li (2000) presented a procedure for preparing a nanofluid which is a suspension

consisting of nano phase powders and a base liquid. Two different kinds of nanofluids are

prepared by varying the base fluid. The first one is the transformer oil based nanofluid which is

prepared by adding Cu nanoparticles by 2 and 5 vol % respectively and the suspension are

stabilized with the oleic acid. The second is the preparation of water based Cu nanofluid in which

Cu nanoparticles are added by 5 vol% and laureate salt is added to stabilize the suspension.

The two-step method for preparing nanofluids is a process by dispersing nanoparticles into base

liquids. This step-by step method isolates the preparation of the nanofluids from the preparation

of nanoparticles. As a result, agglomeration of nanoparticles may take place in both steps,

especially in the process of drying, storage, and transportation of nanoparticles. The

agglomeration will not only result in the settlement and clogging of micro channels, but also

decrease the thermal conductivity (D. Sendil Kumar, 2013).

Simple techniques such as ultrasonic agitation or the addition of surfactants to the fluids are

often used to minimize particle aggregation and improve dispersion behavior. Since nanopowder

synthesis techniques have already been scaled up to industrial production levels by several

companies, there are potential economic advantages in using two-step synthesis methods that
rely on the use of such powders. But an important problem that needs to be solved is the

stabilization of the suspension prepared.

Synthesis of Nanofluids using single step method:

Eastman and Choi (2001) has used a one-step physical synthesis method to prepare nanofluids,

in which Cu vapor was directly condensed into nanoparticles by contact with a flowing low

vapor pressure liquid (ethylene glycol) and the effective thermal conductivity of ethylene glycol

was shown to be increased up to 40% for a nanofluid consisting of ethylene glycol containing

approximately 0.3 Vol% Cu nanoparticles of mean diameter, 10 nm (D. Sendil Kumar, 2013).

Liu et al. (2006) used the technique of chemical reduction method for synthesis of Nanofluids

containing Cu nanoparticles in water without using surfactant as the dispersant. Thus the

synthesized copper nanofluid shows improved thermal conductivity when compared to pure

fluids (D. Sendil Kumar, 2013).

2.3.3 Nano fluids for Refrigeration

The nano refrigerant is one kind of nanofluid and its host fluid is a refrigerant. A nanorefrigerant

has higher heat transfer coefficient than the host refrigerant and it can be used to improve the

performance of the refrigeration systems

There are two methods of improving the thermal conductivity of a nano refrigerant.

The first one is to increase the volume fraction of nano scale materials in the nano refrigerants

and the second one is to use nano-scale materials with high thermal conductivity (Jiang et al.

2009).
2.4 NANOPARTICLES

Nanoparticles are of interest in numerous industrial applications due to their unique and often

advantageous properties. The high surface-to-volume ratio together with size effects (quantum

effects) of nanoparticles introduces many size-dependent phenomena such as chemical,

electronic, magnetic and mechanical properties.

In nanotechnology, a particle is defined as a small object that behaves as a whole unit with

respect to its transport and properties. Particles are further classified according to their diameter.

Coarse particles cover a range between 10,000 and 2,500 nanometers. Fine particles are sized

between 2,500 and 100 nanometers.

Ultrafine particles or nano particles are sized between 1 and 100 nanometers. Nanoparticles may

or may not exhibit size-related properties that differ significantly from those observed in fine

particles or bulk materials. Although the size of most molecules would fit into the above outline,

individual molecules are usually not referred to as nanoparticles. Nano powders are agglomerates

of ultrafine particles, nanoparticles, or nano clusters. Nanometer-sized single crystals, or single-

domain ultrafine particles, are often referred to as nano crystals.

2.4.1 Properties of Nano particles

Nanostructure materials are single phase or multiphase polycrystalline solids with a typical

average size of a few nanometers (1nm = 10-9m).Basically, the range from 1-100 nm is taken as

nano-range for convention as per National Nanotechnology Initiative in the US., and the size of

hydrogen atom is considered as the lower limit of nano whereas upper limit is arbitrary. The

grain sizes are so small; a significant volume fraction of the atoms resides in grain boundaries.

2.4.2 Synthesis methods of Nano particles

Synthesis of nano material is most commonly done based on three strategies

 1. Liquid-phase synthesis

2. Gas-phase synthesis

3. Vapour-phase synthesis

2.5 COPPER OXIDE (CuO) NANOPARTICLES

Nanoparticles research on Copper oxides has been gaining increasing interest due to their unique

properties, such as increased electrical conductivity, toughness and ductility, increased hardness

and strength of metals and alloys, luminescent efficiency of semiconductors, formability of

ceramics.

Copper is a Block D, Period 4 element, while oxygen is a Block P, Period 2 element. Copper

oxide nanoparticles appear as a brownish-black powder. They can be reduced to metallic copper

when exposed to hydrogen or carbon monoxide under high temperature. They are graded

harmful to humans and as dangerous for the environment with adverse effect on aquatic life.

2.5.1 Applications

The key applications of copper oxide nanoparticles are as follows:

1. It is used as burning rate catalyst in rocket propellant. It can greatly improve the homogeneous

propellant burning rate, lower pressure index, and also perform better as a catalyst for the AP

composite propellant

2. It is applied to the catalyst, superconducting materials, thermoelectric materials, sensing

materials, glass, ceramics and other fields.

3. It is used as ceramic resistors, magnetic storage media, gas sensors, near-infrared tilters,

photoconductive and photo thermal applications.

4. It can be used as semiconductors, solar energy transformation, and high-tech superconductors.

2.6 REFRIGERATION SYSTEMS

The main objective of a refrigeration cycle is to remove unwanted heat from one place and

discharge it into another. To accomplish this task, the refrigerant is pumped through a closed

refrigeration system. If the system was not closed, it would be using up the refrigerant by

dissipating it into the surrounding media; but because it is closed, the same refrigerant is used

over and over again, as it passes through the cycle removing some heat and discharging it.

Before treating these practical refrigeration cycles, we consider the Carnot refrigerator, which

provides a standard comparison.

2.6.1 The Carnot Refrigerator:

In a continuous refrigeration process, the heat absorbed at a low temperature is continuously

rejected to the surroundings at a higher temperature. Basically, a refrigeration cycle is a reversed

heat engine cycle. Heat is transferred from a low temperature level to a higher one; according to

the second law, this requires an external source of energy. The ideal refrigerator, like the ideal

heat engine operates a Carnot cycle, consisting in this case of two isothermal steps in which heat

Qc is absorbed at the lower temperature Tc and heat Qh is rejected at the higher temperature Th, and

two adiabatic steps. the cycle requires the addition of net work W to the system. Since the change

in internal energy of the working fluid is zero for the cycle, the first law gives

W= Qh -Qc (Van Ness, M.M. Abbott, 1996)

Types of refrigeration systems

a. Vapour compression refrigeration systems;

i. Domestic refrigeration systems

ii. Air conditioning systems

b. Vapour absorption refrigeration systems

c. Solar energy based refrigeration systems

d. Air cycle refrigeration systems

e. Steam and Vapour jet refrigeration systems

f. Thermoelectric refrigeration systems, and

g. Vortex tubes

Among the above most refrigeration system, most commonly used refrigeration is Vapour

compression refrigeration system.

2.6.2 The Vapour-Compression Cycle

The Vapour compression uses a circulating liquid refrigerant as the medium which absorbs and

removes heat from the space to be cooled and subsequently rejects that heat elsewhere. It is the

most widely used refrigeration cycle.

The figure above depicts the schematics of a typical, single stage vapour compression

system.

Vapour compression refrigeration system and the operating cycle on a T-S diagram. As shown in

the Figure above the standard single stage, saturated vapour compression refrigeration system

consists of the following four processes:

Process 1-2: Isentropic compression of saturated vapour in compressor

Process 2-3: Isobaric heat rejection in condenser

Process 3-4: Isenthalpic expansion of saturated liquid in expansion device

Process 4-1: Isobaric heat extraction in the evaporator

All such systems have four components: a compressor, a condenser, a thermal expansion valve

and an evaporator.
Circulating refrigerant enters the compressor at stage 1 in the thermodynamic state known as a

saturated vapor and is compressed to a higher pressure, resulting in a higher temperature as well.

The temperature of the refrigerant during this isentropic compression process increases well

above the temperature of the surrounding medium. The hot vapour is routed through a condenser

as superheated vapour at state 2 and leaves as saturated liquid at state3 as a result of heat

rejection to the surroundings. The temperature of the refrigerant at this state is still above the

temperature of the surroundings4. The condensed liquid refrigerant, in the thermodynamic state

known as a saturated liquid, is next routed through an expansion valve where it undergoes an

abrupt reduction in pressure. That pressure reduction results in the adiabatic flash evaporation of

a part of the liquid refrigerant. The saturated liquid refrigerant at state 3 is throttled to the

evaporator pressure by passing it through an expansion valve or capillary tube. The temperature

of the refrigerant drops below the temperature of the refrigerated space during the process. A fan

circulates the warm air in the enclosed space across the coil or tubes carrying the cold refrigerant

liquid and vapour mixture. Refrigerant enters the evaporator at state 4 as a low quality saturated

mixture, and it evaporates by absorbing heat from the refrigerated space. The refrigerant leaves

the evaporator as saturated vapour and re-enters the compressor, completing the cycle.

Compression: Compression of a gas causes its temperature and pressure to increase while also

reducing the volume of gases. The compressor is used in a refrigeration system to raise the

pressure of the vaporized refrigerant, causing its saturation temperature to rise, so that it is higher
than that of the atmosphere. The compressor also promotes circulation of the refrigerant by

pumping it around the system.

Isentropic compression: An isentropic process is an idealized thermodynamic process that is

adiabatic and in which the work transfers of the system are frictionless; there is no transfer of

matter and the process is reversible. Isentropic compression takes place If compression of gas

takes place with no flow of heat energy is added or removed from the system. This compression

usually occurs without any change in entropy. An adiabatic process is one in which no heat

Adiabatic compression is expressed by

................(1)

Where k = Cp/Cv = ratio of specific heats, dimensionless.

Although compressors are designed to remove as much heat as possible, some heat gain is

inevitable.

The type of compressor used in refrigeration systems may be reciprocating or centrifugal in

operation. Of the reciprocating, rotary, and centrifugal compressors, the most popular among

domestic or smaller power commercial refrigeration is the reciprocating. The reciprocating

compressor is similar to an automobile engine. A piston is driven by a motor to suck in and

compress the refrigerant in a cylinder. As the piston moves down into the cylinder (increasing the

volume of the cylinder), it sucks the refrigerant from the evaporator. The intake valve closes

when the refrigerant pressure inside the cylinder reaches that of the pressure in the evaporator.

When the piston hits the point of maximum downward displacement, it compresses the

refrigerant on the upstroke. The refrigerant is pushed through the exhaust valve into the

condenser. Both the intake and exhaust valves are designed so that the flow of the refrigerant
only travels in one direction through the system (Moran, Michael J. and Shapiro, Hoaward N.,

1992).

Detail of Compressor Valve Function

Condensation (Constant pressure heat rejection in the condenser): Condensation is the

change of the physical state of matter from gas phase into liquid phase, and is the reverse

of evaporation6. Condensation can technically happen at any temperature, as long as the pressure

of the condensing gas is more than the pressure of the liquid state of that gas (both at the same

temperature). The condenser removes heat given off during the liquefaction of vaporized

refrigerant. Heat is given off as the temperature drops to condensation temperature. Then, more

heat (specifically the latent heat of condensation) is released as the refrigerant liquefies.

Heat of rejection is the energy removed from a refrigerant in the condensing process. Hot

gaseous refrigerant enters the condenser where it loses its latent heat of evaporation to become

hot liquid refrigerant.

Condensing Temperature: The condensing temperature is the temperature at which the

refrigerant gas will condense to a liquid, at a given pressure. It should not be confused with the

discharge temperature, which is the temperature when the superheated gas leaves the compressor.

Condensers are rated in terms of total heat rejection (THR), which is the total heat removed in

de-superheating, condensing and sub-cooling the refrigerant.

Condenser Total Heat of Rejection (THR): Total heat of rejection (THR) is equal to net

refrigeration effect (RE) at the evaporator (compressor capacity) plus the energy input into the

refrigerant by the compressor (heat of compression). The heat of compression will vary

depending on the compressor manufacturer, type of compressor and the operating conditions of

the compressor.

Heat rejection in the condenser may be illustrated on the P-H (pressure enthalpy) diagram. A

pressure enthalpy diagram is used because condensing takes place at constant pressure or nearly

constant pressure when blended refrigerants are used.

The THR of the condenser is defined by line J-H, which is the sum of the refrigeration effect

(line D-F) and the heat of compression line F-H. As the ratio between compressor discharge and

suction pressure increase, the refrigerant effect decreases and the heat of compression increases.

This is because the work done by the compressor has increased.

Expansion valves: Expansion valves are flow-restricting devices that cause a pressure drop of

the working fluid i.e. they remove pressure from the liquid refrigerant to allow expansion or

change of state from a liquid to a vapor in the evaporator. The valve needle remains open during

steady state operation. The size of the opening or the position of the needle is related to the

pressure and temperature of the evaporator. The high-pressure liquid refrigerant entering the

expansion valve is quite warm. This may be verified by feeling the liquid line at its connection to

the expansion valve. The orifice within the valve does not remove heat, but only reduces pres-

sure. Heat molecules contained in the liquid refrigerant are thus allowed to spread as the

refrigerant moves out of the orifice. Under a greatly reduced pressure the liquid refrigerant is at
its coldest as it leaves the expansion valve and enters the evaporator.

Expansion valves controls the amount of refrigerant flow into the evaporator and thus controlling

the superheat at the outlet of the evaporator. The liquid refrigerant leaving the expansion valve is

quite cold. Thermal expansion valves are often referred to generically as "metering devices".

Flow control, or metering, of the refrigerant is accomplished by use of a temperature sensing

bulb, filled with a similar gas as in the system, which causes the valve to open against the spring

pressure in the valve body as the temperature on the bulb increases. As the suction line

temperature decreases, so does the pressure in the bulb and therefore on the spring causing the

valve to close. A sensor bulb, at the end of the evaporator, monitors the temperature change of

the evaporator. This change in temperature creates a change in pressure on the diaphragm.

Evaporation: Evaporation is a type of vaporization of a liquid that occurs from the surface of a

liquid into a gaseous phase that is not saturated with the evaporating substance. In simple terms

evaporation is when a liquid becomes a gas without forming bubbles inside the liquid volume.

Evaporator is the part of the refrigeration system that is doing the actual cooling. Because its

function is to absorb heat into the refrigeration system (from where you dont want it), the

refrigerant is let into and measured by the Expansion valve, and eventually released to the

compressor. An evaporator fan draws air from the refrigerator and blows it over the evaporator

coils. The liquid refrigerant absorbs heat from the air and the air blows back into the refrigerator

at a lower temperature, cooling the refrigerator. The liquid refrigerant starts to vaporize as it

heats up and moves to the compressor (Roy J. Dossat).

REFERENCES

9. D. Sendil Kumar, 2013, Nano-refrigerant for Eco-friendly and clean environment,

Department of Mechanical Engineering, Sri Ganesh College of Engineering and

Technology.

10. Siegfried Haaf, Helmut Henrici, 2002, Refrigeration Technology in Ullmann's

Encyclopedia of Industrial Chemistry.

11. Van Ness, M.M. Abbott, 1996, Introduction to chemical engineering

thermodynamics, 5Th Edition.

12. 5. Moran, Michael J. and Shapiro, Hoaward N., 1992, Fundamentals of

Engineering Thermodynamics.

13. IUPAC, Compendium of Chemical Terminology, (1997) 2nd Edition. Online

corrected version: (2006} condensation in atmospheric chemistry.

14. ASHRAE, ANSI/ASHRAE S tandard 34-2001, Designation and Safety

Classification of Refrigerants. American Society of heating, Refrigerating and Air-

Conditioning.

15. T. Commaressin, K. Palaniradja, 2014, International Journal of Advanced

Mechanical Engineering, Volume 4.

16. William C. Whitman, William M. Johnson, John A. Tomczyk, 2005, Refrigeration

and Air Conditioning Technology.