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# Institution of Chemical Engineers
Trans IChemE, Vol 80, Part C, December 2002

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CALCIUM PHOSPHATE SCALE FORMATION FROM


SIMULATED MILK ULTRAFILTRATE SOLUTIONS
N. ANDRITSOS, S. G. YIANTSIOS and A. J. KARABELAS
Chemical Process Engineering Research Institute, and Department of Chemical Engineering,
Aristotle University of Thessaloniki, Thermi-Thessaloniki, Greece

alcium phosphate deposit formation caused by the ow of SMUF (simulated milk


ultra ltrate) solutions was studied under well-de ned hydrodynamic conditions at 60
and 70 C in the pH range 5.87.0. At 60 C maximum deposit formation of mostly
amorphous calcium phosphate occurs in the pH range of 6.26.4, and at a somewhat lower pH
at 70 C. Above pH 6.3 bulk precipitation occurs, depleting the solution of scale-forming ions
and resulting in reduced deposition rates. At the maximum deposition rate, an initially thin and
well-adhering layer is formed, entirely covering the substrate within minutes from the onset of
ow. Further growth occurs mostly in the form of overgrowths consisting of clusters of
submicron particles. By employing two different pipe diameters, a range of Reynolds numbers
from 7000 to 17,000 was covered. With increasing ow velocity the deposition rate tends to
increase, while more compact deposit layers are obtained. Preliminary experiments provide no
clear evidence that the deposited mass is affected by the surface treatment or the type of
substrate material; however, reduced adhesion to the modi ed surfaces is likely.
Keywords: milk; model uid; fouling; calcium phosphate; pipe ow.

INTRODUCTION

phases: amorphous calcium phosphate [ACP, stoichiometry


corresponding to Ca3(PO4)2xH2O], dicalcium phosphate
dihydrate (DCPD, CaHPO42H2O), octacalcium phosphate
[OCP, Ca8H2(PO4)65H2O], and hydroxyapatite [HAP,
Ca5(PO4)3OH], the least soluble phase27. Whitlokite or
b-TCP [b-Ca3(PO4)2] is also a probable calcium phosphate
phase reported in the literature6. However, this is a high
temperature calcium phosphate phase, which reportedly
does not form at temperatures below 100 C. It is generally
agreed that the formation of HAP from a highly supersaturated solution at neutral pH is usually preceded by ACP
or other precursor phases.
As has been pointed out, fouling in milk processing is a
complicated process because of the phenomena associated
with protein aggregation and deposition as well as mineral
deposition. In particular, calcium phosphate may precipitate
directly on the metallic wall or can be deposited in the form
of particles precipitated in the bulk or associated with milk
proteins5. Nucleation of the calcium phosphate system can
occur both at the wall surface of the heat exchanger and on
casein centres in the bulk7. Barton et al.8 suggested that
calcium phosphate deposition occurred by precipitation
fouling. Several investigators have used model uids to
better understand the effect of solids deposition on milk
fouling. Simulated Milk UltraFiltrate (SMUF), prepared
according to Jenness and Koops9, has been probably the
most commonly used model uid5,10.
The scope of this work, which is part of the European
research project MODSTEEL, is to contribute to further
understanding of the fouling mechanisms upon milk heating
by conducting experiments of calcium phosphate deposition

Fouling of heat exchangers (HE) during milk processing is a


major problem in the dairy industry, with a negative impact
on operating costs and product quality14. Fouling leads to a
rise in pressure drop across the HE (with reduction of the
ow rate) and to possible deterioration of product quality
due to failure of the process uid to reach the required
temperature. Another serious problem associated with fouling is cleaning the fouled surfaces by means of costly and
time-consuming techniques where environmentally offensive chemicals are employed2. Despite the large number of
investigations aiming at elucidating the fouling process and
the success in understanding several aspects of the process,
a real breakthrough in controlling fouling has not been
reached, mainly due to the great complexity of the dairy
system3,5.
Burton1 and other investigators recognize two distinct
types, A and B, of milk deposits. Type A is soft, voluminous
and protein-rich material starting to form at temperatures
exceeding 70 C, reaching a maximum rate at about 100 C.
Type B, the high-temperature deposits, have a hard, compact
and cracked structure, consisting mainly of minerals.
Calcium phosphates constitute a signi cant part of the
milk deposits (up to 80% in type B) and their percentage
tends to increase with temperature. The Ca=P system
equilibrium is quite complex and as a result various calcium
phosphate phases are encountered in the milk deposits,
depending upon the bulk temperature, level of
supersaturation, pH, ionic environment etc. From analysis
of milk deposits calcium phosphate appears in the following
223

ANDRITSOS et al.

224

from model uids excluding the presence of proteins.


Calcium phosphate deposition is studied under controlled
hydrodynamic conditions at temperatures of 60 and 70 C by
the once-through ow of SMUF solutions. A summary of
the MODSTEEL project and of milk fouling in general
can be found in Visser11. Stainless steel AISI 316L is the
standard material of construction of piping and equipment in
the dairy industry. There are numerous reports in the recent
literature that coated or modi ed steel surfaces can help
mitigate the fouling problem in the process industries12,13.
Thus, another objective of this work is to examine the
effectiveness of surface modi cation or coatings in eliminating or reducing scale formation by using SMUF solutions
and the present experimental set-up.

EXPERIMENTAL
Details concerning the experimental set-up, the tubular test
section and the specimen (semi-annular coupons) on which
deposits develop are given in Andritsos and Karabelas14. The
semi-annular coupons are mounted in pairs to give a tubular
test surface arrangement: the tubular test section allows one to
study the fouling process in a well-characterized hydrodynamic system. A schematic of the set-up is presented in
Figure 1. In order to assess the effect of ow velocity, a new
tubular test section was installed (in addition to that already
available, of i.d. 13 mm) comprising of semi-annular coupons
forming an i.d. of 7 mm. These coupons were machined out
of AISI 316L. Some PTFE semi-annular coupons were also
used. Evaluation of the modi ed surfaces was carried out in
another test section placed at the downstream end, having a
10 10 mm2 free cross-sectional area. Modi ed and unmodi ed surfaces of dimension 10 40 mm2 were glued on
special trapezium-shaped stainless steel coupons and inserted
into the test section forming a channel of square crosssection. The unmodi ed at coupons were of stainless steel
AISI 316L with 2R surface nish, provided by UGINE,
France. The following modi ed surfaces were tested:

diamond-like carbon (DLC) coated, Ni-P-PTFE coated,


SiF3 ion implanted and silica coated. The rst three
coupon types were provided by University of Stuttgart,
while the last one was coated in this laboratory. All
coupons were cleaned before use following a standard
cleaning procedure. All at surfaces were characterized
SS G10 contact
by measuring contact angle (in a KRU
angle measuring system) and roughness characteristics
(Ra parameter) with a DEKTAK3 ST pro ler.
The SMUF solutions were prepared with deionized water
and appropriate amounts of the reagents as suggested by
Jenness and Koops9. The nal reagent concentrations are
summarized in Table 1. All reagents were of analytical
grade. The resulting SMUF solution had a pH close to
6.1. For runs at different pH, adjustment was made by
addition of KOH or HCl in reagent solutions 2 and 3,
respectively. The water was rst passed through a lter for
removal of any particulates and then through an electric
heater. The rating of the heater determined essentially the
maximum operating ow rate at 70 C, i.e. 25 ml s 1.
The bulk temperature was measured with a K-type thermocouple located upstream of the test section and controlled within 0.5 C of the desired value. The pH was
controlled within 0.05 units of the desired value. The
pH electrode was standardized before each experiment (and
occasionally during the experiment) with standard buffer
solutions at pH 7.0 and 4.0 at 25 or 60 C. The three reagent
solutions were kept under continuous stirring and were
introduced into the test section via FMI metering pumps.
Cleaning of the test section was carried out by circulating an
acid solution of HNO3 and rinsing with deionized water.
The deposits, after drying at room temperature, were
characterized by powder X-ray diffraction (XRD, Siemens
D500), scanning electron microscopy (SEM, JEOL 6300),
energy dispersion X-ray system (EDXS, OXFORD ISIS
300) and inductively coupled plasma spectroscopy (ICP,
Perkin-Elmer Plasma 40). SEM observations were made
on the modi ed surfaces and on small 10 10 mm2 coupons
after gold sputtering. The speci c surface area of the
deposits was determined by the BET method (Quantachrome). To check the onset and the extent of bulk precipitation, numerous samples were withdrawn during each run
and the solution absorbance was measured at 432 nm in a
spectrophotometer (UNICAM Helios a).

Table 1. Composition of SMUF solutions.


Reagent
Solution 1
KH2PO4
K3 citrateH2Oa
Na3 citrate2H2O
K2SO4
Solution 2
K2CO3
KCl
Solution 3
CaCl22H2O
MgCl26H2O

Figure 1. Schematic diagram of the experimental set-up.

Solution
concentration (mM)
11.61
3.70
6.09
1.03
2.17
8.05
8.98
3.21

Citrate C6H8O73 .

Trans IChemE, Vol 80, Part C, December 2002

CALCIUM PHOSPHATE SCALE FORMATION FROM SIMULATED MILK ULTRAFILTRATE SOLUTIONS 225

RESULTS AND DISCUSSION


Experiments were conducted at two liquid temperatures,
60 and 70 C; two ow velocities were examined simultaneously at each temperature. The pH was one of the main
parameters investigated in this work and was varied between
5.8 and 7.0. In this pH range the solution was supersaturated
with respect to almost all possible calcium phosphate
crystalline phases. The supersaturation ratio of each phosphate phase was determined by
S

IAP
Ksp

where IAP is the ionic activity product of the phase


considered and Ksp the respective thermodynamic solubility
product. The solution speciation and the supersaturation
ratios with respect to several calcium phosphate phases
were computed by the MINEQL computer code15. Figure 2
illustrates the supersaturation ratio of three calcium phosphate phases and of a magnesium one in the pH range of
interest. Although the SMUF solution was supersaturated
with respect to magnesium phosphate, this mineral was not
identi ed in the deposits by XRD and the magnesium
content of the deposits was always less than 1% w=w.
Formation of Deposits
The deposited mass tends to increase with time, as
illustrated in Figure 3 for two typical runs at 60 and 70 C.
The same gure also provides the effect of ow velocity on
the deposited mass. In the great majority of runs an apparent
induction period was identi ed by the delayed appearance of
measurable deposited mass, followed by an increasing
deposition rate, which seemed to become constant at longer
times. The macroscopically observed induction period was in
the range of 520 min. Because of the moderately variable
deposition rate, for the purpose of this work comparison of
deposited mass at different conditions was made at a running
time of 60 min.

Figure 3. Temporal evolution of the deposited mass at two ow velocities


and two temperatures. Circles: pH 6.55, ow rate 42 cm3 s 1. Squares:
pH 6.15. Flow rate 28 cm3 s1.

value, deposits started to form and the deposition rate


increased sharply with a slight increase in pH. Maximum
deposition rate occurred in the pH range of 6.256.35,
where the solution started to become turbid. Above this
pH range the deposited mass decreased, since bulk precipitation (evidenced from increased solution turbidity) relieved
supersaturation and tended to reduce the driving force for
wall precipitation. Figure 4 illustrates this deposition behaviour at 60 C, depicting the mass deposited at 60 min on the
13 mm i.d. semi-annular coupons as a function of pH; the
corresponding initial values of light absorbance were also
plotted. The size and shape of bulk precipitated particles
also depended on pH. At the pH values corresponding to
low absorbance, the particles were relatively large with a
grain-like appearance, but their characteristic size tended to
be reduced to less than 50 nm at higher pH, as shown in
Figure 5. EDXS showed that these particles consisted of Ca,

Effect of pH and Temperature

At 60 C and at pH lower than 6.0 no deposits were


observed for a running time less than 2 h. Above this pH

Figure 2. Supersaturation ratios of phosphate minerals in the pH range of


interest.

Trans IChemE, Vol 80, Part C, December 2002

Figure 4. The deposited mass at 60 min run time vs pH, and the
corresponding change in initial light absorbance. T 60 C, V
0.32 m s 1, i.d. 13 mm (Re 8800).

226

ANDRITSOS et al.

Figure 5. Size and shape of bulk precipitated calcium phosphate particles at 60 C collected on 0.2 mm polycarbonate membrane lters. Left: pH 6.25;
right: pH 6.4.

P and O, while XRD analysis indicated an amorphous phase


and poorly crystallized HAP.
At 70 C the deposition behaviour followed that obtained
at 60 C, with the maximum being shifted to lower pH by
0.10.2 pH units. As expected, the deposited mass increased
with increasing temperature due to enhancement of driving
force and mass transfer. The maximum deposition rate at
70 C was about 1.3 times higher than that at 60 C. It is
further noted that, working at only two temperatures, the
activation energy of the process could not be estimated.
Morphology and Characterization of Deposits
At the maximum deposition rate, the sequence of deposit
formation shown in the micrographs of Figure 6 proceeded
as follows: initially, a thin (less than 1 mm) and welladhering layer was formed very quickly (i.e. in less than
5 min) covering almost entirely the substrate [Figure 6(a)].
Further growth occurred mostly in the form of overgrowths
[Figure 6(b)], developing rather randomly on the covered
substrate. It is noted that these two deposit formation stages
resembled those reported on the deposition of calcium
phosphate colloids on a rotating disk11. The overgrowths
did not appear to be compact and consisted of submicron
spheroids of sizes less than 100 nm, as shown in Figure 6(c),
forming tightly packed clusters. The small size of the
particles comprising the deposits was also re ected in the
large values of speci c area of the deposits (>80 m2 g1).
This type of deposit on the stainless steel coupons was not
removed by simple water rinsing, but they could be removed
rather easily by mechanical means when the deposits were
dry, leaving the adhering initial layer on the substrate. When
these overgrowths exceeded a certain surface density and
mass, i.e. at relatively long times, they tended to form large
deposit ridges, which appeared to be normal to the ow
direction [Figures 6(e) and (f)] with heights up to 200 mm.
These ridges, appearing mainly in the lower part of the pipe,
did not usually cover the whole circumference of the 13 mm
tube for runs up to 2 h. However, they did so in the smaller
diameter section. Very often, the initial layer exhibited
microscopic cracks, which seemed to increase at higher
pH and upon electron beam irradiation. It is likely that
these cracks developed during the drying process.
EDXS and ICP analysis show that the major constituents
of the deposits were P, O and Ca, with small quantities of Mg,

Cl and K. ICP analysis of deposits at 60 C gave a molecular


ratio Ca=P about 1.5, typical of ACP. This stoichiometric
molar ratio may also be attributed to the formation of
precursor phases (DCPD and=or OCP), which rapidly hydrolyse to the thermodynamically more stable HAP. The XRD
patterns of deposits formed at 60 and 70 C are illustrated
in Figure 7. The main HAP peaks are also shown in the
gure. At 60 C an apparent lack of crystalline order is
evident, although a broad peak at about 32 can be observed.
This peak is intensi ed at 70 C, where poorly crystallized
HAP can be identi ed. Visser and Jeurnink4 also reported that, upon heating of SMUF solution at 60 C in the pH
range 67, HAP is formed, preceded by a precursor phase,
which at pH 6.7 is OCP.

Figure 6. SEM micrographs of the mostly amorphous-like deposits formed


at pH 6.3 and 60 C ( ow velocity 0.32 m s1) at various run times
indicated on the pictures. Micrographs (b), (d) and (f) are viewed at an angle
of 60 . Micrograph (c) presents a detail of the deposit overgrowths.

Trans IChemE, Vol 80, Part C, December 2002

CALCIUM PHOSPHATE SCALE FORMATION FROM SIMULATED MILK ULTRAFILTRATE SOLUTIONS 227

Figure 7. XRD patterns of deposits formed from SMUF solutions with and
without citrates.

At pH values lower than that corresponding to the


maximum deposition rate, only parts of the substrate were
covered by an amorphous-like adhering deposit, as illustrated in the micrographs (a) and (b) of Figure 8. On the
other hand, at higher pH values the initial layer had a
powdery appearance, did not cover the substrate entirely
and did not seem to adhere rmly to the substrate
[Figure 8(c) and (d)].
On the Mechanisms of Scale Formation
The above microscopic observations, coupled with
deposition and turbidity measurements, suggest that calcium
phosphate scale formation from SMUF solutions essentially
occurs in a relatively narrow pH range and that at low pH
values the deposits result from direct wall crystallization. As
pH and supersaturation ratio increase, bulk precipitation

starts to occur almost instantly upon mixing of the reagent


solutions. Bulk precipitation consumes a portion of scaleforming ions, thus reducing the driving force for crystallization on the tube wall. The calcium phosphate particles
and aggregates can be transported and deposited onto the
substrate or on the deposit layer, but at rates considerably
lower than those of individual ions (on the basis of the same
mass concentration). This is due to much lower diffusivities
(and mass transfer coef cients) of the colloidal particles
compared with those of ions. The particulate deposits adhere
less strongly on the pipe surface that the deposits crystallizing directly on the wall, as observed experimentally.
Similar deposition behaviour has been also observed with
other scaling systems14.
Apart from the reduced rate of particulate deposition,
another aspect that may be of interest is whether particles
formed by bulk precipitation experience any signi cant
electrostatic forces that could prevent them from depositing
on the developing deposit layer. To address this question,
z-potential measurements were performed by employing the
cylindrical cell of a Rank Brothers Mark II electrophoresis
apparatus. Particles taken from deposits formed at pH 6.7
were dispersed in a 0.1 N KCl solution (close to the ionic
strength of the SMUF solution), with the pH adjusted to 6.7.
At these conditions the particle z-potential was found to be
approximately 15 mV. A simple estimate of the potential
of interaction F between two particles may be obtained from
the relation
F

AH a
2pee0 c2 a ln 1 ekh
12h

where AH is the Hamaker constant, a the particle radius, h


the particle separation distance, e the water dielectric
constant, e0 the vacuum dielectric permittivity, c the particle
surface potential and k the inverse Debye length. At the
particular ionic strength employed, the Debye length is
1 nm. Assuming a typical value of 10 20 J for AH and
using the determined z-potential for c, the potential of
interaction is found to be purely attractive over all separation
distances, as shown in Figure 9. Hence, electrostatic forces
are not expected to play any signi cant role in particle
deposition. This is mainly due to the relatively high ionic
strength, which effectively screens such forces between
owing and deposited particles.
Effect of Flow Velocity
Flow velocity is one of the most important parameters in
fouling. It was recognized very early that velocity affects

Figure 8. SEM micrographs of deposits formed at 60 C at relatively low


and high pH. (a) and (b) pH 6.05, run time 60 min; (c) pH 6.7, run time
20 min; (c) pH 6.7, run time 83 min.

Trans IChemE, Vol 80, Part C, December 2002

Figure 9. Normalized interaction potential between two particles of size a.

ANDRITSOS et al.

228

the fouling process with respect to both deposition and


removal stages and that, in general, high velocities may
reduce deposit formation (due to increased detachment),
something that is true especially for particulate fouling.
However, in the cases where precipitation fouling occurs,
leading to compact and adherent deposit layers (thus minimizing the removal process), high ow velocities result in
higher deposition rates16,17.
In the present experimental system, an increase in the ow
velocity tends to signi cantly increase the amount of deposited mass, at least for the duration of these experiments,
which is less than 2 h, as shown in Figure 3. Although testing
of ow velocity effects is limited to only two values, it may
be deduced that the deposited mass depends on ow velocity,
as V n. The exponent n is approximately 0.7 0.05 (after
correcting for the different pipe diameter), close to that
theoretically expected for a mass transfer-controlled process,
i.e. 0.87516. Certainly, more data are needed to elucidate the
effect of ow velocity Furthermore, it is pointed out that
the in uence of velocity is also pronounced regarding the
morphology of deposits. At the higher velocity, the deposits
are more compact (i.e. they can be removed with much
greater dif culty), the deposit ridges are shorter (or the
surface becomes smoother) covering almost the whole pipe
circumference and leaning in the downstream ow direction. A video image of such deposits appears in Figure 10.
The smoother appearance of the deposits with increasing
velocity has also been observed in other scaling systems,
such as CaCO317,18.
Assessment of Modi ed Surfaces
Preliminary experimental results on the in uence of the
substrate (shown in Figure 11) indicate that the substrate
material and the modi ed surfaces do not exhibit any
discernible difference with respect to deposited mass and
deposit morphology, suggesting that the interfacial properties

Figure 10. Video image of the morphology of deposits in the 7 mm i.d. pipe
section. Conditions: T 60 C; running time 100 min; pH 6.3;
Re 16,000 (V 1.10 m s 1).

do not control the scale formation process. This behaviour


may be explained by considering the aforementioned formation of the initial compact and adhering layer due to wall
crystallization. Once this layer forms, the nature of the
substrate is unlikely to affect the subsequent deposit
formation. The measured roughness average, Ra, of all
surfaces tested is relatively low and is also given in Figure 11.
In the present experiments, smaller amounts of deposits
were systematically obtained on the top coupon, regardless
of the substrate material or surface modi cation. The only
difference that can be observed among the different coupons
is that the probability of having cracks (after drying) in the
initial coherent layer was greater in most of the modi ed
surfaces than in unmodi ed ones (see micrographs in
Figure 12). It is also of interest, that, although the mass of
deposits on PTFE semi-annular coupons was similar to that
on the stainless steel ones, the initial layer on the former
coupons could be easily removed by mechanical means.

Figure 11. Mass of deposits on modi ed and unmodi ed surfaces at various conditions. Each number corresponds to the position of the coupon in the test
section ( ow velocity 0.32 m s1).

Trans IChemE, Vol 80, Part C, December 2002

CALCIUM PHOSPHATE SCALE FORMATION FROM SIMULATED MILK ULTRAFILTRATE SOLUTIONS 229

Figure 12. SEM micrographs of the deposits on different substrates from the same run (T 60 C, pH 6.25, run time 1 h, Re 8800).

This might be interpreted as an indication of reduced


strength of adhesion of scale onto the non-metallic substrate.
Several investigations have also found that the substrate
material becomes unimportant after the formation of
the initial layer1921. Britten et al.19 found that non-metallic
surfaces did not affect the amount of deposits upon milk
heating at 100 C, but the material affected the strength of
adhesion. Yoon and Lund20 reported no effect of surface
materials (electropolished stainless steel, 304 stainless steel,
titanium, polysiloxane and Te on) on calcium phosphate
fouling. More work is certainly needed before a nal
assessment on the ability of modi ed surfaces to reduce
fouling is made.
Contact angle measurements with three different liquids
(water, a-bromonaphtalene and glycerol) were used to obtain
the surface energy parameters of the modi ed surfaces22,
namely the apolar Lifshitzvan der Waals component (gLW)
and the acidbase polar component (gAB). The latter consists
of the electron donor (g ) and the electron acceptor component (g). Comparison of the different surfaces suggests that
the apolar component is approximately the same for all
surfaces and close to 40 mJ m2 and the electron acceptor
component is close to zero for all surfaces. The electron
donor component is the one which differentiates the surfaces
into low-energy (0 mJ m2) for the NiPPTFE coated,
medium-energy (1530 mJ m2) for the DLC coated and
high-energy (4050 mJ m2) for the ion-implanted and
silica-coated surfaces.
In uence of Citrates
It is well known that citrates present in the milk act as
crystal growth inhibitors of the phosphate minerals, through
their complexation to calcium ions5,23 and, possibly, through
other mechanisms (threshold and=or dispersing effects). It is
also likely that other organic substances in small or
large quantities (such as casein) play an inhibitory role
to stabilize various colloidal and dissolved species. This
is probably the reason why SMUF solutions are less stable
than milk and whey upon heating5,23.
Runs with SMUF solutions in the absence of citrate ions
lead to some interesting ndings. First, the maximum
deposition rate is shifted towards a signi cantly lower pH
value. Second, the deposited mass is signi cantly higher
than that obtained in the presence of citrates, as shown in
Figure 13. Third, the deposits after the coupon removal had
a gel-like appearance. XRD and SEM results show that the
phase composition and the morphology of these deposits
Trans IChemE, Vol 80, Part C, December 2002

Figure 13. Comparison of the maximum deposited mass from SMUF


solutions in the presence and absence of citrates (T 60 C, V
0.32 m s 1, Re 8800).

are different, as illustrated in Figures 7 and 14, where platelike DCPD and OCP can be identi ed along with HAP.
Citrates, at much lower concentrations, have been reported
to inhibit crystal growth and induce habit modi cations of
calcium phosphate precipitating in supersaturated solutions24. It is stated that these phenomena were caused by
surface absorption of negatively charged ions.
CONCLUDING REMARKS
Experiments have been carried out to investigate the
mechanism of calcium phosphate deposition from SMUF
solutions at 60 and 70 C, by using tubular test sections.
At both temperatures the deposition rate vs pH exhibited a
bell shape, with the maximum corresponding to the onset
of system bulk precipitation. Under the present experimental
conditions it seems that mass transport plays an important
role in the scale formation and may control the whole
process. An increase in ow velocity leads to more compact
and smoother deposits. Our preliminary experiments
suggests that surface modi cation does not result in noticeable deposit reduction, but some indications exist that
adhesion strength on modi ed surfaces might be smaller,
possibly facilitating clean-up. However, more experiments
are required to investigate scaling characteristics of modi ed
surfaces and obtain more de nitive results.

ANDRITSOS et al.

230

Figure 14. Left, picture from a stereomicroscope (magni cation 40) and, right, SEM micrograph of deposits formed from SMUF solution without citrates
(T 60 C, pH 5.7, Re 8800).

Finally, it is suggested that, since fouling and cleaning


processes are interrelated and can be tackled by employing
the same physicochemical considerations, the present experimental set-up and procedures can also be used to assess the
mechanisms and ef ciency of common cleaning techniques.
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ACKNOWLEDGMENTS
The paper is dedicated to the memory of Dr H. Visser, the coordinator
and the driving force behind the MODSTEEL project, who will be
remembered by the present authors for his contributions in the area of
fouling, his enthusiasm for research and above all his kindness. This work
has been nancially supported by the Commission of European Communities under Contract G5RD-CT-1999-00066. The authors wish to thank the
Analytical Laboratory of CPERI for the XRD spectra and the SEM pictures
and Professor P.G. Koutsoukos of the University of Patras, Greece, for
helpful suggestions and discussions.

ADDRESS
Correspondence concerning this paper should be addressed to
Dr N. Andritsos, CPERI=CERTH, PO Box 361, GR 570 01, ThermiThessaloniki, Greece.
E-mail: andritso@cperi.certh.gr
The paper was presented at the Fouling, Cleaning and Disinfection in
Food Processing conference held at the University of Cambridge, UK, 35
April 2002. The manuscript was received 31 May 2002 and accepted for
publication after revision 29 October 2002.

Trans IChemE, Vol 80, Part C, December 2002

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