Geothermics, Vol. 18, No. 1/2, pp. 83-88, 1989.

Printed in Great Britain.

Calcium Carbonate

0375-6505/89 $3.00 + 0.00

Pergamon Press plc

Scale Formation

Evangelos

Dalas

on Heated Metal Surfaces

and Petros G.Koutsoukos

Department of Chemistry and the Research Institute of Chemical Engineering and High Temperature Chemical Processes.
P.O. Box 1239, University Campus, GR-26 ii0 Patras, Greece

Abstract.Geothermal water utilization is seriously hindered by the development

of insoluble calcium carbonate formation.The nature of the polymorphs formed
is strongly dependent on the solution conditions and the substrate on which
scale is deposited. The employment of a flow-system in which supersaturated
calcium carbonate solutions flowed through pipe specimens made of various
materials such as 316 stainless ste~l
or aluminum, and heated externally at
temperatures ranging from 50vC to 80UC,revealed that the salt formed
initially
on the pipe walls was vaterite. Surface energies computed from kinetics data
showed an increase with temperature from 36.7 to 59.2 mJ m-2.The activation
energy was found to be 36 kJ mole -I suggesting a surface controlled mechanism.

Introduction
Calcium carbonate, in its various polymorphic occurrences is frequently
encountered in thermal springs and geothermal wells. These formations, are
cases which may be studied from the equilibrium point of view
(Cowan and
Weintritt, 1976). In systems where scale deposits occur as a result of usage
of raw water, the deposition takes place on already existing surfaces. More
specifically, in the process of utilization of geothermal energy, extensive
scale formation in the pipelines and pumps employed may cause severe
problems
in the operation of geothermal power plants and even cause interruptions of their
operation. Depending on the chemical composition of the water of the geothermal wells, calcium carboante and silica deposits are the main insoluble minerals encountered. Calcium carbonate formation is more important in the geothermal wells in Greece, where the soil is rich in calcium carbonate rendering
waters of high degrees of hardness.
The problem of understanding the m e c h a n i s m of calcium carbonate formation
is of key importance in controlling and prevention of this undesired deposit.
It should be noted that calcium carbonate is encountered in a number of polymorphic phases including (in decreasing solubility order) calcium carbonate
monohydrate, vaterite, aragonite and calcite. The conditions under which
these polymorphs are formed are very sensitive to factors such as temperature
(Kitano, 1962), the presence of foreign ions in solution (Giannimaras
and
Koutsoukos, 1988) and to the substrate on which heterogeneous nucleation and
growth takes place (Dalas and Koutsoukos 1988). In the present work we have
attempted to investigate the nature of the calcium carbonate phase precipitating and the mechanism of its formation under flow conditions, through pipe
specimens of various materials of construction
The effect of temperature on
the precipitation process and the role
of the material of construction of
the pipe specimens employed was investigated. The possibility of scale inhibition by means of diphosphonates was also studied.

83

Evangelos Dalas and Petros G. Koutsoukos

84

Experimental
Calcium carbonate supersaturated solutions, volume totalling 0.2 dm 5 were
prepared in_a double walled water jacketed, pyrex glass vessel thermostatted
at 25.00.iUC by mixing equal volumes of calcium nitrate and sodium bicarbonate solutions
made fresh for
each experiment (Giannimaras and Koutsoukos
1987). The pH of the supersaturated solutions was adjusted at 8.50 by the
addition of standard potassium hydroxide. The solution pH, measured
by a
combination glass/saturated calomel electrode (Metrohm)was constant for time
periods exceeding the fourty eight hours, demonstrating
the stability of the
solution. The electrode was calibrated before and after each experiment with
NBS buffer solutions. Following the verification of the stability
of
the
supersaturated solutions for two hours after mixing, the solution was circulated by means of a peristaltic pump through a pipe specimen. The specimens
employed were made of : Aluminum, Aluminum covered by glass internally and
of stainless steel. The length of the specimens was 0.07 m, the I.D. 4 mm and
the O.D
6.5 mm. The total specimen area was 8.8xi0 -4 m 2. The pipes were
heated externally by a heating mantle and the temperature was measured in the
walls and
in the center of the tubes by a thermocouple. Prior to their use
in the flow through system, the pipe specimens
were
cleaned
in a ultrasonic
bath
of
distilled
acetone
for
30 minutes
and then dried at i02C for
15 min. The
flow-rate,
of
the
supersaturated
solutions
pumped
through the tubes was 37.5 ml min-l;
a reynolds
number
of Re=286 ensured
laminar flow. The tubing was selected so that the dead volume (6.6 ml) is
minimal. Upon exiting
the tube, the solution was cooled by a condenser cooled
by tap water. The temperature difference between the inner and the outer walls
was maximum 0.6C. At the highest wall temperature (80C) the heat flux from
the heated wall to the cooler flowing liquid was 3.1 cal/s.
At 50Oc the
heat flux was 1.4 cal/s.
After cooling, the supersaturated solution was
returned to the main glass reservoir. As
could be
seen from the stability of
the supersaturated solutions, no deposition took place
as
long
as
the
specimens
were
not heated. Following
heating
of
the
specimen walls and
after the lapse of a certain induction perod, the deposition of calcium
carbonate in the walls of the tubes started, resulting in a decrease in pH.
This pH decrease, triggered the addition of sodium carbonate, sodium bicarbonate and calcium
nitrate titrant solutions from two mechanically coupled burettes of an
appropriately
modified titrator (Dalas and Koutsoukos 1988), so
that the solution composition could be maintained. The constancy of
the
solution composition was verified by sampling, filtering through membrane
filters (0.i ~Lm, Gelman) and analyzing the filtrates for calcium by atomic
absorption spectroscopy (Varian 1200). The solid phases were examined
by
infrared spectroscopy (Perkin Elmer 177) by scanning electron microscopy (SEM,
JEOL JSM-35) and by powder x-ray diffraction (Philips
1300/00). The experimental set-up employed is illustrated in Fig.l. The concentrations of titrant

I
pH meterI ~j~~

~!~
I

PUSl 1 o I

REC

MS ]

Fig. I' Experimentol set-up

REC:IMPLS:
recorderimpulsmat
MS~magnetic stirrer
CE: combinotion
electrode
P: peris,ol,ic pump
S : specimen
C : condenser

Scale Formation on Heated Metal Surfaces

85

solutions were made as described in detail elsewhere ~ i a n n i m a r a s and Koutsoukos

1 9 8 8 ) H y d r o x y e t h y l i d e n o I-i diphosphonic acid solutions were made from stock
solutions (Monsanto)neutralized with the addition of standard potassium hydroxide)
Results

and Discussion

Under our experimehtal conditions (small dead volume and high flow rate)
we ensured that the flow is laminar and the thickness of the liquid in which
the temperature drop (from the walls to the center of the tube) occured
was
estimated to be 0.5 mm max. This thickness is smaller than the thickness of
the stationary layers, 6 h = 0.54 mm. The temperature and hence the supersaturation gradient occu~ed therefore at the stationary layers and it may be
considered constant. The temperature of the flowing supersaturated solution
at the center of the tubes was m e a s u r ed to be 25C. Along the length of the
specimens we have observed a temperature difference between the entrance and
the exit of the circulating supersaturated solution never exceeding t h o u g h
the 2C. This difference would not affect our kinetics data. The solution
speciation, a prerequisite for the calculation of
the
degree
of
super,
saturation at various temperatures, was done from the equilibria for
the various carbonate species, mass balance equations and the e l e c t r o n e u t r a l i t y
conditions as described elsewhere (Koutsoukos and Kontoyannis 1984). The
temperature
dependence of the equilibrium constants for the calcium
and
carbonate species was taken from the literature (Plummer and Busenberg 1982)
and the activity coefficients
were calculated by an extended Debye-H~ckel
equation (Davies
1962) . The change in Gibbs free energy, AGx, for the formation of each polymorphic phase, x, was calculated from equation (i):

AG

(Ca2+)t(CO~-)t
= _ R_~T in
= _ R_~T inn
x
2
(Ca2+)e,x(CO
2
x
~-)e,x

(I)

In equation (i) ( )
denote activities, and the subscripts t and e refer
to time t and equilibrium, for the polymorph considered, respectively. The
initial conditions of the experiments in the present investigation are summarized in Table i. The reproducibility in the induction times, r, obtained
was better than 5% and the rates of crystallization estimated from the rates
cf titrants addition as a function of time were reproducible within 7%. The
deposition of calcium carbonate occured on the heated metal surface, apparently from the supersaturation gradient established in the stationary layer,
adjacent to the heated metal walls. It should be noted that when the
tube
specimens were not heated, no deposition occured, for at least five hours of
flow-through circulation of the supersaturated solutions.
Under our experimental condition, it was verified by powder x-ray diffraction and by infra-red spectroscopy that the initially forming phase
is
vaterite, as it may be seen in Fig.2. This is in agreement with Other studies,
in which we have shown that when s p o n t a n e o u ~ p r e c i p i t a t i o n occurs vaterite is
the initially forming phase, converting to the thermodynamically more stable
calcite (Xyla and Koutsoukos 1987). It should be noted that the verification
of the formation of the unstable vaterite is made possible because of the
fact that the solution supersaturation is kept constant. As
may
be seen
from the results presented in Table i, the rates of precipitation of vaterite
onto the heated 316 stainless steel walls depended strongly
not only on the
wall temperature but on supersaturation as well. The rates were taken at the
beginning of the deposition thus
reflecting the rate of vaterite formation.
In supersaturated solutions (~>i) the rate of crystallization R may be
written as a power law of the solution supersaturation:
R = kn n

(2)

In equation (2) k is a rate constant and n a constant, called the apparent

rate order. Logarithmic plots according to eq.(2) are shown in Fig.3. At all

Evangelos Dalas and Petros G. Koutsoukos

86

t e m p e r a t u r e s (50-80C) the same v a l u e n:6 was o b t a i n e d for the a p p a r e n t orde~

of r e a c t i o n thus p o i n t i n g to the same, s u r f a c e c o n t r o l l e d m e c h a n i s m for the
d e p o s i t i n g phase. M o r e o v e r , the h i g h v a l u e of the r e a c t i o n o r d e r n, p o i n t e d
to a p o l y n u c l e a r m e c h a n i s m (Nyvlt et al. 1985). The s u r f a c e e n e r g e y c o m p u t e d ?
a c c o r d i n g to this m o d e l for the d e p o s i t i n g v a t e r i t e r a n g e d from o = 7 6 . 8 m J m-at 50oc to o = 1 4 7 . 6 1 m J m -2
at 80oc. T h e s e v a l u e s are t y p i c a l for s p a r i n g l y
s o l u b l e salts. M o r e o v e r , an a p p a r e n t a c t i v a t i o n e n e r g y of 36 k J / m o l e was
o b t a i n e d for v a t e r i t e , w h i c h is c l o s e to the v a l u e r e p o r t e d for c a l c i t e
( K a z m i e r c z a k et al. 1982) and p o i n t s to a s u r f a c e c o n t r o l l e d m e c h a n i s m .
_

T a b l e i: C r y s t a l l i z a t i o n of C a l c i u m C a r b o n a t e on H e a t e d S t a i n l e s s S t e e l 316
S u r f a c e s ; pH 8.50. T u b e s u r f a c e area (internal) : 8.8xi0 -4 m 2. T o t a l calcium,
Cat= T o t a l c a r b o n a t e , C t
Exp.
#
25
26
27
28
21
22
23
24
17
19
18
20
16
14
13
15

Temp.
oc
5O
50
50
50
60
60
60
60
70
70
70
70
80
80
80
80

Ca t
/xl0-3M

Induction
time ~
min
25
i00
160
260
17
50
120
210
15
44
i00
192
i0
30
90
196

3.50
3.00
2 5O
2 00
3 5O
3 00
2 5O
2 00
3 50
3 00
2 50
2 00
3 50
3 00
2 5O
2 00

AG~

AG A

AG c

Rate
/xl0-5mol min-lm-2

-3 i0
-3 02
-2 91
-2 76
-3 36
-3 28
-3 16
-3 01
-3 61
-3.53
-3.41
-3.25
-3.87
-3.78
-3.66
-3.49

7.5
5.0
3.0
1.7
9.2
5.7
3.3
1.9
9.6
6.4
3.6
2.1
11.7
7.1
3.9
2.4

kJ m o l -I
-1.54
-1.46
-1.35
-1.20
-1.82
-1.74
-1.62
-1.47
-2.09
-2.01
-1.89
-1.73
-2.36
-2.28
-2.16
-1.99

-2.71
-2.63
-2.52
-2.37
-2.97
-2.89
-2.78
-2.62
-3.23
-3.14
-3.03
-2.87
-3.49
-3.40
-3.28
-3.12

* S u b s c r i p t s to the c h a n g e in free e n e r g i e s d e n o t e : V = v a t e r i t e , A = a r a g o n i t e
C = c a l c i t e . R a t e s are c a l c u l a t e d per unit g e o m e t r i c s u r f a c e area.

~0

40

80

20

~000 2000 1400 400

:~0 o
woven umber/cm -~
Fig,:): a. powderXIRD spectra b. IR spectra
of calcium carbonates and scale 4eposit

Scale Formation on Heated Metal Surfaces

87

The material of construction of the specimens

influenced only the
induction periods, which were longer for the aluminum specimens, but the rates
of deposition were not significantly different.
When the stainless steel specimens were equilibrated with neutralized
EHDP (10-3moi dm -3) for 48 h, under conditions ensuring homogeneity of the
aqueous phase, EHDP was adsorbed on their surface. When, following extensive
washing so as to ensure that no EHDP was coming out of the metal surface
(by following conductivity of the aqueous phase and analyzing for total
phosphate), the specimens were tested with respect to calcium carbonate deposition, it was found that not only the rates of crystallization were reduced
but the induction times were markedly extended. The results of the inhibitor
treatment of the specimens are shown in Table 2. It may be seen that depending
on the initial concentration of EHDP pretreatment, the rates obtained were

4.0

50C

60C

_70C.0 80~C

4..1'

4~,
D::

{:~

_o

4.,~

I1.7
I
0,4

I
O. 8

.*
O.S

I
0.7

too 1'],
FiO~: Kinetics of colcium corbonote s~ole form(]tlon
almost 1000 times lower than the rates corresponding to the untreated samples,
and induction times increased from 60-670%.
The conclusion from the present investigations are that CaCO 3 deposition
on heated metal surfaces is surface controlled and the initially forming
phase is vaterite, its formation resulting from the supersaturation gradient
established. The material of the specimen ~employed is important only with
respect to the time required for the formation of the critical nucleus. Finally, pretreatment of the specimens with inhibitor, such as diphosphonates, may
cause not only extension of the induction times but retardation of rates of
deposition as well.
~ab.le 2. Effect of EHDP pretreatment of stainless steel 316 specimens with
respect to calcium carbonate deposition. Cae=~ Ct = 3.00x10-3mol dm -3, 80oc,
pH 8.50 surface area of specimens 8.8xi0 -4 m 2.
Exp.

.EHDP*

Induction time,r

mol dm -3

min

/xl0-8mol min-lm -2

38

1 x 10 -3

200

8.3

39

1 x 10 -4

160

9.6

40

1 x 10 -5

64

12.5

41

1 x 10 -6

48

14.2

*Concentration of the EHDP solution during pretreatment

88

Evangelos Dalas and Petros G. Koutsoukos

References
Dalas, E. and Koutsoukos, P.G. (1988) The crystallization of vaterite on
cholesterol. Langmuir. In press.
Davies, C.W. (1962) Ion Association. pp 37-48. Butterworths, London.
Cowan, J.C. and Weintritt, D.J. (1976) Water Formed Scale deposits.
pp. Ii0-iii. Gulf Publ~Co. Houston, Texas.
Giannimaras E.K. and Koutsoukos, P.G. (1988) Precipitation of calcium
carbonate in aqueous solutions in the presence of oxalate anions. Langmuir,
In press.
Kazmierczak, T.F., Tomson, M.B. and Nancollas G.H. (1982) Crystal Growth
of Calcium Carbonate. A controlled composition kinetic study. J.Phys.Chem.
86, 103-107.
Kitano, Y. (1962) Polymorphic formation of calcium carbonate in thermal
springs with an emphasis on the effect of temperature. Bull. Chem. Soc.
Japan 35, 1973-1980.
Koutsoukos P.G. and Kontoyannis, C.G. (1984) Precipitation of calcium
carbonate in aqueous solutions. J.Chem. Soc.Farad. Trans. I, 80, 1181-1192.
Nyvlt, J., S6hnel, 0., Matuchova, M. (1985) The kinetics of Industrial
Crystallization. pp. 186-189. Elsevier. Amsterdam/Oxford/New York/Tokyo.
Plummer, N.L. and Busenberg, E. (1982) The solubilities of calcite,
aragonite and vaterite in CO2-H20 solutions between 0 and 90oc and an
evaluation of the aqueous model for the system CaCO3-CO2-H20. Geochim.
Cosm. Acta 46, 1011-1040.
Xyla A.G. and Koutsoukos P.G. (1987) The precipitation of calcium carbonat~
in Aqueous solutions. 31st Int. Congress of Pure and Applied Chemistry,
Sofia Bulgaria, July 1987 Posters 3 section 7 p.743.
Acknowlegments
We gratefully acknowledge support of this project by the European Communities
Grant No ENG-0036-GR.