1

CHAPTER - 1
1. INTRODUCTION
1.1 WATER ITS SIGNIFICANCE AND SOURCES
Water often termed as universal solvent, comprises threequarters of the surface of the earth. Even though, a significant portion of
our planet is covered with water, most of it is not usable in the form we
find it. Our use is focused on freshwater, which comprises only about 3%
of all the water found on earth. The remaining 97% is sea/saltwater,
which is not considered suitable for industry, agriculture or domestic
use. It is estimated that 70% of freshwater resources are locked as ice
and glaciers at our poles, on mountaintops as glaciers and snow pack
and in the ground as permafrost. These resources are out of our reach
and therefore we are left with a very small 1% (Fig. 1.1) of the water on
earth as usable surface water or groundwater. This fraction of the
earths water resources supports all terrestrial life and powers our
industries [1].
With the invention of the steam engine, the use of water took on a
completely new set of applications. It became an inevitable material for
transportation of thermal energy from one place to another. The
industrial revolution has made the use of freshwater more significant.
Agrarian and domestic use of a water resource had to give way to these
industrial needs. Globally, about 70% of the water we use is for

agriculture. Industry consumes 22%, and our domestic use rounds out
the balance at 8% [1].

Fig. 1.1 Breakup of water resources on earth [1]

Problems associated with deposition and corrosion, in early use of
steam from low pressure industrial process boilers and steam locomotive
engines revealed the need of water treatment. Development of more
sophisticated and complicated industrial processes have resulted in
ever-increasing water quality demands in order to meet process needs.
However, the treatment that was effective in one location was not
necessarily effective in another. The difference was due to the
characteristics

of

the

source

water

and

it

became

clear

that

understanding the variability of different raw water characteristics is

essential to tailor a chemical solution.
The major sources of fresh water are surface water and ground
water. Surface water supply includes rivers, lakes, reservoirs, etc.
Groundwater is water stored between layers of rock or in sand beds
underground. The ground water supply is obtained either from deep or
shallow wells. Water quality of both surface and groundwater can be
affected by both anthropogenic natural forces such as rainfall, geological

characteristics, seasonal changes, pollution, introduction of non native

species, construction of dams on rivers etc. The surface water generally
contains high amount of dissolved oxygen and sediments and low
amounts of dissolved solids. Ground water on the other hand, contains
high amounts of dissolved solids and low amounts of suspended solids
and dissolved oxygen. Irrespective of its origin, water always contains a
complex mixture of organic and inorganic substances, most of which are of
natural origin resulting from complex interaction between water, soil and
underlying

geological

strata

and

from

complex

biological

and

microbiological processes occurring in soil and water [2]. These factors

can determine how water is to be treated, the type and size of various
water treatment schemes and equipment needed to make the water
useful for a particular applications etc.

1.2 TREATMENT METHODS

Raw water contains different types of impurities in varying
amounts. Before this water can be used for common industrial or
household applications, it requires treatment to remove these impurities.
There are two types of treatment methods i) External treatment ii)
Internal treatment.

1.2.1 EXTERNAL TREATMENT METHODS

As the name indicates external treatment methods are carried out
before water enters into equipments such as boilers/heat exchangers
etc. They include Coagulation, Flocculation, Filtration, Ion Exchange
treatment (softening, demineralization) etc.

1.2.1.1 COAGULATION AND FLOCCULATION

Turbid water contains suspended matter with varying particulate
sizes. Settleable solids are particles large enough to settle quiescently,
while dispersed solids are particles that do not readily settle. Water
clarification is the process of removal of suspended solids from water. A
significant portion of non-settleable solids may be colloidal, stabilized by
negative electrostatic charges on its surface, causing it to repel
neighbouring particles. Coagulation is the destabilization of these
colloids by neutralizing the forces that keep them apart. This is generally
accomplished by adding chemical coagulants with appropriate mixing
energy. Aluminum salts (Alum, Sodium aluminate), iron salts (Ferrous
sulphate, Ferric chloride), and polyelectrolytes are the chemicals usually
used [3].
While coagulants are smaller molecules designed to neutralize the
surface charge on the particle, flocculants are polymers having very high
molecular weight and require an inversion or dissolution step before
being used to bridge particles. Flocculation is promoted by slow mixing,
which brings the flocs gently together. Excessive mixing velocity shears
the floc, and they seldom reform to their optimum size and strength
without additional polymer treatment.

1.2.1.2 FILTRATION
Water filtration is a batch-type liquid-solids separation process for
the removal of suspended material by passing it through a porous bed of
sand or other granular materials. Sand filters have been used for many

years as a final polishing step in municipal and industrial water plants.

Granular media filtration is used to remove suspended solids from raw
water, recycled water, floc particles from pre-treated water, precipitates
from the effluent of a lime or lime-soda ash process etc. The most widely
used granular media filter is the conventional rapid sand type filter with
either a single media (sand) or a dual media (activated charcoal-sand)
bed. Pretreatment filters used in industry for large-scale applications are
usually of the conventional type with dual media. For smaller industrial
filtration applications, such as boiler water pre-treatment and recycle,
pressure filtration systems are usually employed. Filtered suspended
solids are usually removed from the filter by backwashing the media,
and draining the waste backwash water.

1.2.1.3 ION EXCHANGE

Since water has been used in industrial processes, deposits from
undesirable ionic species have been precipitating on equipment resulting
in reduction of heat transfer [4-10]. Ion exchange is a reversible process,
an exchange of one ion for another, (example Na+ or H+ for Ca2+) using a
synthetic resin. As water passes through the resin, exchange of ions
occurs, undesirable ions (Ca2+/Mg2+ etc.) from the water are removed
and replaced with desirable ions (Na+/H+) that have been loaded on the
resin. Which ions are loaded on the resin and which ions are exchanged
are determined by the application and the type of resin loaded in the
vessel. Once exhausted, the resin bed can be recharged with desired ions
through a process called regeneration. Ion exchange process is most

widely used in industries for softening and demineralising water. It

received utmost importance due to its regeneration facility using very
cost effective chemicals.

1.2.1.4 MEMBRANE FILTRATION

Membrane filtration is based on the approach for the transport of
substances

between

two

fractions

with

the

help

of

permeable

membranes. The most popular membrane technologies used today are

microfiltration (MF), ultra-filtration (UF), reverse osmosis (RO) and
nano-filtration

(NF).

MF

and

UF

are

pressure-driven

membrane

separation techniques used for separating particles, including bacteria,

from liquid streams. The MF/UF membranes have pores through which
water and some solids pass. Separation is based on size exclusion,
where particles larger than the pore size are retained by the membrane
and particles smaller than the pore size pass through. MF can remove
particles about 0.1 m in size. Specifically, MF membranes can be
prepared with definite pore sizes, ranging from about 0.05 to 2 m, such
that particles of interest can be removed from solution by selecting the
MF membrane with the proper pore size. The pore size of the UF
membrane ranges from 0.1 to 0.001 m [1]. RO and nano-filtration NF
are similar, pressure driven membrane separation techniques used to
separate dissolved solids from solution. RO and NF are used for a wide
variety of applications, from seawater desalting for drinking water and
electric power generation to makeup pre-treatment for boilers and
cooling tower systems.

1.2.2 INTERNAL TREATMENT IN BOILERS

The primary reason for the formation of scale in boilers and heat
exchangers is that the solubility of the scale forming salts in water
decrease with raise in temperature, pressure and concentrations [11-18].
The thermodynamic driving force for the formation of a new phase is the
supersaturation of the solution [19-24]. In a boiler, as vapour leaves the
boiling water, the dissolved solids originally in the water are left behind.
The water left behind becomes increasingly concentrated, and eventually
reaches a level where further concentration could cause deposits of scale
to form or result in problems with steam quality. Table.1.1 lists the
various scales commonly found in feed water and low-pressure boiler
systems [25].
Even the best feed water treatment systems allow some solids to
pass into the boiler/heat transfer equipments. During such situations,
addition of chemicals to boiler feed water (often referred as internal
treatment), becomes essential to prevent scale formation. Scaling
elements such as calcium, magnesium, iron, etc., are controlled by
addition of carbonate or phosphate or chelating agents or a combination
of these [26]. While carbonate programme leaves behind lot of sludge,
phosphate residual treatment programs are best suited for feed waters
that are consistently below 60 mg/L hardness and have low magnesium.

Table.1.1 Crystalline scale constituents identified by X-ray diffraction

Name

Formula

Acmite

Na2OFe2O34SiO2

Analcite

Na2OAl2O34SiO2.2H2O

Anhydrite

CaSO4

Aragonite

CaCO3

Brucite

Mg(OH)2

Calcite

CaCO3

Cancrinite

4Na2OCaO4Al2O32CO29SiO2.3H2O

Hematite

Fe2O3

Hydroxyapatite

Ca10(OH)2(PO4)6

Magnetite

Fe3O4

Noselite

4Na2O3Al2O36SiO2SO4

Pectolite

Na2O4CaO6SiO2.H2O

Quartz

SiO2

Serpentine

3MgO2SiO2.2H2O

Thenardite

Na2SO4

Wallastonite

CaSiO3

Xonotlite

5CaO5SiO2.H2O

Chelating agents control metal ions by forming complex with the

metal ion, preventing it from entering into its normal (and in many cases
undesirable) reactions. Metals chelated by chelating agents are still
present in the system. They are inactivated because their reactive sites
are blocked and, therefore, they can no longer undergo reaction or cause

reactions in the system. It is generally proposed that the main action

mechanisms

of

this

scale

inhibitor

are

chelating

effect,

lattice

deformation and electrostatic repulsion [27]. Among these mechanisms,

lattice deformation caused by scale inhibitor can well explain the low
dose effect of scale inhibitor, and is widely accepted. However, there is
no confident proof to show how scale inhibitor deforms the lattice, since
Buchrer suggested this mechanism in the 1950s [27]. It is also not clear
whether chelating agents work in a similar way to all the scale causing
elements. Hence, in order to understand the mechanism of formation of
scale and its preclusion, it is essential to have a clear knowledge on
crystal growth form an atomistic approach.
1.3 CRYSTAL GROWTH AND MORPHOLOGY
As mentioned earlier, the thermodynamic driving force for the
formation of a new phase is the supersaturation of the solution. Once
supersaturated, the primary particles can grow from solution but need a
nucleus to grow from. In heterogeneous nucleation, since a surface is
already present, it is less energetically demanding. On the other hand, in
homogeneous nucleation, the nucleus forms spontaneously from the
solution itself when a critical supersaturation is reached. The nucleation
of a new layer starts from surface nucleation of an island on the plane
face, which grows further by attachment of further atoms/ions to the
steps and kinks of the new layer until the surface is completed. The flat
surfaces of a crystal grow via layer-by-layer adsorption of solute atoms
or molecules onto an existing crystal face. This layer-by-layer growth

10

mode of a crystal surface is expressed in the model of Kossel [28].

However, the growth of a surface is rarely perfect, and a number of
imperfections exist in the form of vacancies or dislocations. As a
consequence, growth steps are not as ideal as implied by the Kossel
model but are fuzzy [29].
Under equilibrium conditions, the micro- and macro-shape of
single crystals is related to the intrinsic structure of the unit cell, and
the crystal shape can reflect the unit-cell replication and amplification.
However, the surface morphology often varies significantly from the
shape of the unit cell. From a thermodynamic viewpoint, the diverse
morphologies of the same mineral are due to the differences in surface
energies of the crystal faces, which in turn are dependent on the external
growth environment. Faces with low surface energies will grow slowly
and dominate the final shape whereas faces that have high surface
energies will grow quickly and vanish completely upon crystal growth to
the final morphology. This treatment assumes that the equilibrium
morphology of a crystal is defined by its minimum surface free energy,
which can be calculated as the sum of the products of surface energy
and surface area of all exposed faces [30]. According to this rule, the
shape of crystals will be affected by changing the surface energy of the
surfaces. If this can be done in a face-selective way, the equilibrium
morphology of a crystal can be tuned in a defined and predictable way.
For this, various additives, i.e., inorganic ions or organic additives can
be used [31-39]. This strategy of crystal morphogenesis has been

11

recognized for a long time and has even found industrial application
mainly based on empirical observations [40-49].
1.3.1 POLYMORPHISM
Polymorphism is the ability of a solid material to exist in more than
one crystal structure, and it has been recognized for centuries [50-52]. It
has great technological significance as the behaviour such as hardness,
optical properties etc., depends on the solid-state structure [53].
Polymorphism is important in many fields like agrochemicals, pigments,
dyestuffs,

foods,

and

explosives

and

is

especially

relevant

for

pharmaceutical compounds because dissolution rates depend on the

polymorph [54].
Since different polymorphic forms of same substance have
different properties, polymorphism plays an important role in controlling
the scale formation using chelating agents or any chemicals used in
internal treatment. For example, it is obvious from Table.1.1 that the
predominant polymorphic form of calcium carbonate in scale is calcite
and vaterite is seldom present [25]. However, one of the long-standing
challenges in crystallization is the ability to predict and control the
polymorphism.
1.4 CALCIUM CARBONATE (CaCO3)
The design and fabrication of inorganic materials with well
controlled morphology have recently attracted a lot of interest because of
their potentials in the design of new materials and devices [46, 55-64].
Many strategies have been developed for the controllable synthesis of

12

nanomaterials with various morphologies and sizes [65-75]. CaCO3 is a

mineral abundantly found in nature and has gained much attention due
to its significance in industrial applications, biomineralization etc [50,
76-79]. In cooling water system and boiler tubes, it is one of the most
predominant components of hard and tenacious scale, which has a
substantially bad influence on heat transfer. It exhibit three anhydrous
polymorphs

(trigonal

calcite,

orthorhombic

aragonite,

and

orthorhombic/hexagonal vaterite, in order of decreasing stability at

ambient

conditions)

and

two

hydrated

polymorphs

(monoclinic

hexahydrate ikaite and CaCO3 monohydrate) [44, 57, 80-85]. While

usual morphology of calcite is rhomboidal, aragonite is needle like and
vaterite forms polycrystalline spheres [86-90]. Since the three anhydrous
CaCO3 polymorphs have different characteristic morphologies, control of
the crystal polymorph provides a route to controlling morphology.
Traditional strategies for selection of polymorphs often involve changing
solvents, temperature, usage of polymer additives and other growth
conditions in an attempt to control crystal formation by changing from
thermodynamic toward kinetic control or vice versa [72, 91-97].
Crystal growth of CaCO3 with various morphologies in the
presence of four kinds of amino acids, (L-Cystine (L-Cys), L-Tyrosine (LTyr), DL-Aspartic Acid (DLAsp), L-Lysine (L-Lys) and the mixed systems
of L-Tyr (or L-Lys)/Mg2+, has been reported by Xie et al. [98]. The results
have shown that calcite was formed in L-Cys system while both calcite
and spherical vaterite with various morphologies were produced in the
presence of L-Tyr, DL-Asp. The study indicated that amino acids played

13

an important role in the process of crystal growth of CaCO3 and the

addition of Mg2+ was helpful for the formation of aragonite.
Chen et al. have reported that 1,3,5-trialkylbenzenes (TMB) can be
employed to change the morphology and polymorph of CaCO3 crystals in
the presence of sodium dodecyl sulfate (SDS). Their studies revealed that
at 90 and 120 C, TMB induced the formation of vaterite. They have also
reported that aragonite was first produced, which transformed to the
vaterite, and later the vaterite is transformed to calcite, through the
dissolution-recrystallization processes [99].
A systematic examination of the influence of various experimental
parameters on the morphology and size of CaCO3 particles at room
temperature in the presence of poly sodium 4-styrene-sulfonate (PSSS) is
reported by Lei et al. The studies reveal that PSSS could be used as an
effective crystal growth modifier to control the crystallization of CaCO3 at
room temperature. They have observed that with increase in pH, the rate
of crystallization was faster and hence the morphological control of the
crystals were less and the electrostatic interaction between the polymer
and surfactant is an important factor in the crystallization of CaCO3
particles [100].
Studies on electrochemical synthesis of CaCO3 coatings on
stainless steel substrates are done by Dinamani et al. They have
reported that the morphology of the deposit varies from facetted rhombs
at low current densities (1 - 20 mA/cm2) to corner rounded particles at
higher current densities (40 mA/cm2) [101].

14

A new route for the synthesis of vaterite from pure calcite was
been

reported

by

Dupont

et

al.,

by

using

108

mol

dm3

Hydroxyethylidene-1, 1-Diphosphonic acid (HEDP) at 95 C in the

presence of ultra- sonic waves. The data suggests that HEDP plays the
dual role of surfactant and stabilizing agent in the synthesis of CaCO3 [102].
Preparation of monodispersed cubic CaCO3 composite particles in
the presence of Polyacrylic acid (PAA) at different concentration of PAA
(1.0 - 2.0 g/l), CaCl2 (4 - 16 mM) at pH (10) and temperatures
(60 - 80 C) were reported by the Cheng et al. The results revels that
variations in the concentration of PAA and CaCO3, molar ratio of PAA to
CaCO3, and pH and temperature of solution drastically influence the
morphology of the CaCO3 particles, but all the samples consisted calcite
crystals [103].
Studies done by Euvrard et al., on the optical characterization of
CaCO3 crystals developed on metallic surfaces by using Polymaleic acid
(PMA) and Polyaspartate (PASP) revealed that PASP and PMA can affect
the crystallization of CaCO3 at low concentrations (110-5 mol dm-3).
These polyelectrolytes interact on the crystallization of CaCO3 and can
modify the crystallization of CaCO3 [104].
Yang et al., have reported crystallization of CaCO3 between 120
and

135

(0.3

MPa)

under

N2

atmosphere

in

Poly(ethyleneoxide)poly(propyleneoxide)poly(ethyleneoxide)

presence

of

triblock

copolymer and O-(Hydroxy isopropyl)chitosan. Their study revealed that

the occurrence of calcite was predominant with less concentration of

15

these chemicals and as the concentrations of polymers increase, the

average particle size become smaller and the increase of polymer
concentration favours the formation of spherical vaterite in the presence
of both the polymers [105].
Similarly, Shen et al., have also reported the crystallization of
CaCO3 at 26 C for 10 h in the presence of Polyvinylpyrrolidone (PVP)
and Sodium dodecylbenzene sulfonate (SDBS) individually and also with
blended system of these chemicals. The results revealed that the mixture
of PVP and SDBS resulted in schistose calcite, ellipsoidal calcite and
spherical vaterite depending upon both the total concentration and ratio
of PVP to SDBS. The synergistic effect of PVP molecules and SDBS in the
reactive crystallization systems controls the crystallization habit of
CaCO3 by affecting the morphology and polymorphs of CaCO3 [106].
Shen et al., have synthesized Hydrolyzed polymaleic anhydride
(HPMA) and studied its effect on the precipitation of CaCO3. The
synergistic effect of synthesized HPMA with HEDP and PAA on the
crystal of CaCO3 was also investigated. The results revealed that in the
presence of HPMA or PAA and HEDP framboid like and sponge like
calcite and vaterite were formed respectively. In the presence of
HEDP/HPMA/PAA both framboid and sponge like calcite and vaterite
were noticed along with regular rhomboidal calcite. They have also
reported that the order of the ability to prevent the precipitation of Ca2+
from bulk solution was HEDP/HPMA/PAA>HEDPHPMA>PAA [107].

16

Crystallization of CaCO3 was carried out in the presence of

surfactant mixtures, SDS and Hexadecyl(trimethyl)azanium bromide
(CTAB) at 90 C at different time intervals by Chen et al. They have
reported that the CaCO3 crystals changed from flower like vaterite to
aragonite via dissolution-recrystallization mechanism with increase in
reaction time and when the concentrations of CTAB is increased keeping
the concentrations of SDS constant [108].
Zhang

et

al.,

have

reported

the

CaCO3

scale

inhibition

mechanisms based on the effect of different scale inhibitors HEDP,

Aminotrimethylenephosphonic acid (ATMP), 2-Phosphonobutane-1,2,4tricarboxylic (PBTC), Acrylic acid/acrylic ester copolymer, Acrylic acid/2hydroxypropylacrylate/2-acrylamido-2-methylpropanesulfonic

acid

copolymer and Phosphino maleic anhydride polymer. The studies revels

that in the absence of scale inhibitors, meta-stable phases usually
transform into stable phase as calcite. When scale inhibitors are added,
both formation and transformation of meta-stable phases are inhibited,
which resulted into the occurrence of aragonite and vaterite [27].
Inhibition of CaCO3 scale has been investigated in the presence of
three

inhibitors-PAA,

ATMP

and

Polyamino

polyether

methylenephosphonate (PAPEMP) at 60 C by Tang et al., Their study

revealed that ATMP shows the threshold effect in the inhibition of
CaCO3 scale, but PAA and PAPEMP do not; thus scale inhibition
behaviour of PAPEMP is similar to that of PAA. The normal growth of
CaCO3 is disturbed in the presence of inhibitors, but in the presence of

17

PAPEMP, the scale morphology is similar to that of the presence of

ATMP. PAA and ATMP can kinetically prevent vaterite from transforming
to aragonite and calcite, but PAPEMP cannot [109].
A study has been carried out by Ketrane et al., on the efficiency of
five commercial scale inhibitors; sodium hexametaphosphate (HMPS),
MEDPHOS, sodium tripolyphosphate (STTP), Polyphosphonate (SECAL)
and Polycarboxylic acid - sodium polycarboxylate (RPI2000) on CaCO3
precipitation. They have reported that these inhibitors are capable of
preventing CaCO3 precipitation between 20 to 40 C and Phosphonates
are

better

inhibitors

than

Polycarboxylates

or

Polyphosphates

particularly at 50 C [110].
Inhibition of CaCO3 precipitation has been reported by Lal et al.,
by using amino polyphosphonate (Ethylenediamine-N,N,N1,N1,tetrakis
(methylenephosphonic acid)) (EDTMP) at different concentrations. The
results revealed that amorphous CaCO3 (ACC) precipitates from
supersaturated solution and transforms to crystalline polymorphs
(calcite and vaterite) in solution and then, the meta-stable polymorph
(vaterite) transforms to calcite. They have also reported that the effect of
EDTMP on the transformation of vaterite to calcite in the bulk solution is
much stronger than that on the transformation of ACC to crystalline
polymorphous [111].
The kinetics of CaCO3 (calcite) dissolution between 3.3 - 12 pH in the
presence of calcium chelating agents 1,2-Cyclohexanediaminetetraacetic
acid

(CDTA),

Diethylenediaminepentaacetic

acid

(DTPA)

and

18

Ethylenediaminetetraacetic acid (EDTA) was investigated and reported by

Fredd et al. The results showed that (1) the dissolution rate of calcite is
increased significantly in the presence of these chelating agents in the
order CDTA>DTPA>EDTA (2) the rate of dissolution is influenced by the
kinetics of the chelation reactions and varies considerably with pH and
type of chelating agent [112].
An abnormal structural transformation from calcite to aragonite
has been reported with increase in temperature from 90 to 120 C in the
presence of a mixed system of Cetyltrimethylammonium bromide (CTAB)
and Polyacrylamide (PAM) by Nan et al. The results suggested that such
mixed systems, can be a promising candidates for crystal growth
modifiers [113].
The effect of calcium complex chelating agents like Citric acid
(CIT), DTPA, EDTA and Pyromellitic acid (PMA), and their concentration
on the induction time of CaCO3 nucleation has been studied at 50 C by
Westin et al. [114]. They have reported that the induction time was
found to increase with additive concentration and CIT caused maximum
increase in induction time and PMA the least. This was attributed to the
interfacial energy as CIT, DTPA and EDTA caused a notable increase of the
interfacial energy where as PMA had no effect on the interfacial energy.
Yu et al., studied the crystallization behaviour of CaCO3 particles
from

aqueous

solutions

in

the

absence

and

presence

of

PAA,

Polyethylene glycol (PEG) and Polyvinyl alcohol (PVA) and CTAB at 25 C

and 80 C. The studies revealed that organic additives and temperatures

19

obviously influence the crystal forms and morphologies of CaCO3.

Various shapes of CaCO3 polymorphs, such as, plate, rhombohedra,
ellipsoids, whisker and dendrite were also reported [56].
Similarly, phase transformation of CaCO3 in the presence of
Calcium dodecyl sulfate (CDS) and urea aqueous solutions was studied
by Nan et al. The experiments were carried out at 120 C at different
time intervals up-to 48 h. They have reported novel morphologies for
vaterite (tabular sphere-shaped, bicone-shaped, dumbbell-shaped) and
phase transformations from vaterite to calcite and aragonite, and from
calcite to aragonite [115].
The effect of three green inhibitors Carboxymethyl inulin (CMI),
PASP and PMA along with organic additive Polyphosphinocarboxylic acid
(PPCA) on bulk precipitation of CaCO3 and on the deposition on the
surface of austenitic steel at 70 C under a controlled turbulent flow
regime was investigated by Setta et al. The study states that full
inhibition of CaCO3 requires higher concentrations for scale deposition
than for scale precipitation. A comparison between green inhibitors and
organic additives revealed that these green inhibitors require higher
concentrations to reach efficiency of PPCA [116].
It is also reported that the presence of chelating agents have a
significant

role

on

the

crystalline

structure

and

morphology.

Morphosynthesis of CaCO3 at different reaction temperatures and the

effects of Poly-diallyldimethylammonium chloride (PDDA), CTAB and
EDTA has been reported. The study reveals the presence of these

20

additives greatly suppress the formation of aragonite. Among these

additives, EDTA was the one that showed the most prominent effects on
particle morphology of CaCO3. The sequence of pH adjustment is
reported to be a critical factor for the additive functionality [117].
Similarly, electrochemical synthesis of BaCO3 from a solution of its
bicarbonate in the presence of various chelating agents (like DTPA,
EDTA and NTA (Nitrilotriacetic acid)) on stainless steel substrates shows
different morphology and oriented crystallization growth [118]. These
sequestrants are widely used in industries for keeping CaCO3 in
suspension and thus as scale inhibitors in boiler feed water.
Polymorphism in CaCO3 plays a vital role in scale formation and
its inhibition [52, 53]. Reports suggests that, in the presence of scale
inhibitors, substantial amount of vaterite and aragonite occur in scale,
while in the absence of scale inhibitors, calcite is the most predominant
crystal form [26, 27]. Moreover, for the scale inhibitor with higher
inhibition efficiency, more vaterite and aragonite are present in scale
[27]. Since the order of stability of the crystalline phases are calcite >
aragonite > vaterite, generally meta-stable phases convert into stable
phases. Polymorphic transformations of CaCO3 following the Ostwald
step

rule

(first

nucleated

as

the

meta-stable

spherical

vaterite

polymorph, and then transform gradually into the stable rhombohedral

calcite polymorph) has been already reported [119-122]. Although
presence of calcite brings the greatest thermodynamic stability under
different conditions, the thermodynamically less stable aragonite and

21

vaterite phases may be stabilized under certain temperatures/conditions

in the presence of some additives/inhibitors [123-129].

1.5 SUMMARY OF THE LITERATURE

The above literature survey clearly demonstrates that reaction
conditions are of great importance not only for selection of the
crystallization pathway but also for determining the mechanism by
which the final crystal will be formed and how its morphology will be
influenced. The experimental variables, which are directly related to the
supersaturation are reactant concentration, presence of inhibitors, pH,
temperature, or pressure etc., as they determine the amount of dissolved
species in solution. It is also understood that there are many reports on
morphological studies and polymorphism on CaCO3, a major constituent
in scale. However, a comprehensive study by correlating the differences in
morphology or polymorphic composition with the formation/preclusion of
scale while using inhibitors, particularly above 100 C, is lacking.

1.6 OBJECTIVE OF THE WORK

To understand the process of building up of the scale from an
atomistic level and its preclusion, it is essential to study the formation of
each constituent (such as CaCO3, Mg(OH)2, SiO2, etc.) in the scale
independently and then synergistically, in the presence of each additive
under different conditions.

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1.7 SCOPE OF THE WORK

As a prelude to the above exercise, this work was designed to
synthesize CaCO3, the most predominant component in scale, in the
presence of five different chelating agents; EDTA, NTA, N-(hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), DTPA and HEDP. To know the
synergistic effect of these chelating agents, it was proposed to carry out
the synthesis in combinations also. As the aim of this investigation was
to understand the formation of CaCO3 scale and its preclusion, it was
proposed to conduct experiments at 60 and 80 C in open beakers
(situations such as in cooling towers) using a rotamantle for heating. To
simulate conditions prevailing in heat exchangers and boilers it was
proposed to carryout synthesis between 100 and 230 C in closed high
pressure

autoclaves.

Considering

boiler

blow

down

TDS

of

3500 - 5000 ppm, the synthesis were proposed to be carried out from
0.1 M CaCl2.
In order to determine the most appropriate system for a particular
temperature, it was proposed to characterize the CaCO3 samples using
powder X-ray diffraction (XRD), Raman spectroscopy, Fourier transform
infrared spectroscopy (FT-IR) and scanning electron microscope (SEM)
techniques. The details of these investigations, experiments performed
and the conclusion drawn are described in the following chapters.