Journal of Food Engineering 73 (2006) 379387

www.elsevier.com/locate/jfoodeng

The eect of citrate on calcium phosphate deposition from

simulated milk ultraltrate (SMUF) solution
Roxane Rosmaninho *, Lus F. Melo
LEPAE, Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
Received 27 September 2004; accepted 5 February 2005
Available online 7 April 2005

Abstract
As has been widely reported, dierent calcium phosphate phases can be formed in solution depending on several physical-chemical aspects like the concentration of free calcium and phosphate ions, pH of the solution, temperature and the presence of interfering ions. The present work aims at studying the eect of pH and of citrates on the precipitation of calcium phosphate in a
solution that simulates the mineral composition of milk (SMUF), as well as the subsequent eect on the deposition on stainless steel
surfaces. The dierent calcium phosphate species formed during heating at dierent pH values and in the presence or absence of
citrate were characterized by scanning electron microscopy, X-ray microanalysis and X-ray diraction. Their fouling behaviour
was characterized according to the amount of deposit formed on stainless steel surfaces and to the deposit
s resistance to removal
by hydrodynamic shear forces. The absence of citrate was responsible for the decrease in the solution pH and for the formation of a
crystalline dicalcium phosphate dihydrate structure with a deposited mass which was almost twice the one obtained in the presence
of citrate.

2005 Elsevier Ltd. All rights reserved.
Keywords: Milk fouling; Citrate; Hydroxyapatite; Dicalcium phosphate dihydrate

1. Introduction
Fouling in milk processing is a complex process because it involves several simultaneous phenomena associated with protein aggregation and subsequent
deposition and mineral salts deposition, the latter
mainly caused by calcium phosphate (Jeurnink, Walstra,
& deKruif, 1996). It has not yet been claried whether
calcium phosphate fouling is due to deposition of particles which have been formed in the bulk, or due to direct
crystallization/precipitation on the surface (Andritsos,
Yiantsios, & Karabelas, 2002). Therefore, the fouling
process must be analysed not only in terms of deposit

Corresponding author. Fax: +351 22 5081449.

E-mail address: roxane@fe.up.pt (R. Rosmaninho).

0260-8774/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.02.017

adhesion and growth but also according to what is happening in the bulk solution.
The most widely used test solution in milk mineral
deposition studies is called simulated milk ultraltrate
(SMUF) which was rst described by Jenness and
Koops (1962). It is a simplied milk system which constitutes, so far, the best way to evaluate the role of the
dierent milk mineral components on the overall milk
fouling behaviour. Due to the use of this simplied system more is now known about the mechanisms of fouling of the dierent milk components but there are still
remaining some key scientic problems related to the
poor understanding of the role of some interfering ions
such as citrate (also present in SMUF) on the precipitation behaviour of calcium phosphate under dierent pH
values.
Calcium phosphate formation by precipitation from
solution is determined by two mechanisms which only

380

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

occur under supersaturated solutions: (i) nucleation and

(ii) crystal growth. The latter is composed of several
steps, starting with transport of ions from the bulk solution to the nuclei surface, followed by adsorption on
energetically favourable sites.
The formation of calcium phosphate nuclei and,
afterwards, the precipitation phenomenon are only observed after a dened concentration of the correspondent ions in solution is reached. That concentration,
the solubility, varies with the overall solution conditions. In solutions containing calcium and phosphate,
a number of calcium phosphate phases may be formed
(Fig. 1), depending mainly on the pH and calcium concentration. As a result of that, calcium phosphate precipitation will depend on the phase closest to
saturation at the prevailing solution conditions. However, in environments which mimic milk, urine or other
natural biological solutions, the interactions caused by
other ions are signicant and the solubility isotherms
can only be used as a starting point for prediction of
the forming phase. The goal of this work is to obtain advances on the interactions between citrate ions and calcium phosphate in simulated milk solutions, in order to
better understand the formation of unwanted deposits
on surfaces and to design appropriate cleaning
strategies.
There are a wide range of calcium phosphate phases
that may precipitate, most likely as precursors to
hydroxyapatite (HAP), as defended by several authors
(House, 1999; Liu, Sethuraman, Wu, Nancollas, &
Grynpas, 1997; Milev, Kannangara, & Ben-Nissan,
2003; van Kemenade & de Bruyn, 1987; Visser & Jeurnink, 1997), namely dicalcium phosphate dihydrate or
brushite (DCPD), octacalcium phosphate (OCP), tricalcium phosphate (TCP) or amorphous calcium phos-

Fig. 1. Calcium phosphate solubility isotherms (Vereecke and Lemaitre, 1990).

phate (ACP). It is well established that kinetic factors

may be of great importance in determining the characteristics of the phases formed during the precipitation
process together with equilibrium considerations. In
other words, what is thermodynamically the most stable
phase may not be the one which precipitates rst because its precipitation kinetics is slower. The formation
of the dierent calcium phosphates species can consequently be explained by kinetic, thermodynamic or solubility eects, or on the other hand be the result of the
interactions with other substances present in solution.
Little is currently known about the conditions or levels
of supersaturation necessary to produce precipitation
in the last case, more precisely to overcome the eect
of organic ligands, because not much is yet known about
the interactions between those organic molecules and
the calcium phosphate compounds formed in solution.
A number of kinetic studies have attempted to establish the specic conditions for the formation of each precursor phase, most of them having been carried out
under the constant composition method (Koutsoukos,
Amjad, Tomson, & Nancollas, 1980). Ions such as magnesium have also been reported as important inhibitors
for the precipitation of certain phases, by forming chemical complexes with the newly formed surfaces, blocking
further precipitation (Abbona & Franchiniangela,
1990). Some studies do exist assessing the eect of organic ligands like citrate and acetate on the precipitation
of dicalcium phosphate dihydrate (DCPD), octacalcium
phosphate (OCP) and hydroxyapatite (HAP). In seeded
solutions, they all reported inhibition of hydroxyapatite
precipitation by adsorption of the organic molecules on
active growth sites of the seeding material, resulting in
the formation of phospho-citrate complexes (van der
Houwen & Valsami-Jones, 2001). This inhibition eect
of citrate on calcium phosphate kinetics was rst presented in an earlier study, at the time concerned with
the inhibition eect on the transformation of OCP into
any other more stable crystalline form (Sharma, Johnsson, Sallis, & Nancollas, 1992). Some work concerning
the role of citrate on calcium phosphate precipitation
from a SMUF solution was also presented in a recent
publication by Andritsos et al. (2002) at pH values
and temperatures dierent from those tested in the present paper and whose conclusions will be discussed later.
Although considerable work has been done on calcium phosphate precipitation and on the preferential
precipitation phases, the majority of those studies was
carried out in low ionic strength solutions, mainly composed of calcium and phosphorous. In the present work,
the study of the dierent calcium phosphate phases
formed under heating treatment and in the presence of
citrate was evaluated for a solution which simulates
the mineral composition of milk. The nal goal is to
contribute to the understanding of the fouling process
in milk pasteurization processes.

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

381

2. Materials and methods

The experimental work described here was focused
on the eect of citrate on the precipitation behaviour
of calcium phosphate from a milk simulating solution
upon heating. Special attention was given to: (i) the type
of calcium phosphate structures precipitated in the bulk;
(ii) the type of deposit formed on stainless steel surfaces.
To detail the eect of citrate on the deposition behaviour, two dierent solutions were used: (1) SMUF solution (containing citrate), prepared with deionised water
and appropriate amounts of the reagents (analytical
grade), following the recipe of Jenness and Koops
(1962), whose stequiometrical nal composition is summarized in Table 1. The solution had a pH of 6.30 after
preparation and was adjusted to 6.80 with KOH or to
6.15 with HCl as desired. (2) modied SMUF solution
(without citrate). This last solution had a pH of 6.15
immediately after preparation and no pH adjustment
was performed in this case.
The fouling behaviour of the dierent solutions was
evaluated by performing deposition experiments on
stainless steel surfaces (316 2R nish) and evaluating:
(i) the amount of deposit formed on the surface by
weighing (analytical balance AND GR-200); (ii) the
structure of the deposits formed on the surface by scanning electron microscopy observation (JEOL
JSM6301F), (iii) their chemical composition by X-ray
microanalysis (Noran Voyager) and (iv) the percentage
of deposit mass detached from the surface by hydrodynamic forces at the temperature and pH used during
the deposition stage.
Before each deposition experiment, the stainless steel
samples used as deposition surfaces were cleaned with a
commercial detergent (RBS35 from RBS Chemical
Products) according to the following procedure: (1)
samples were immersed in a 2.0% w/v detergent
(RBS35) solution in distilled water at 65 C for 5 min;
(2) rinsed with distilled water at 65 C for 5 min and
(3) rinsed with distilled water at 20 C.
The experiments were performed with a rotating disk
apparatus (Fig. 2) to study the fouling behaviour of cal-

Table 1
Composition of the SMUF solution
Reagents

Concentration in solution (mM)

KH2PO4
K3 citrate H2Oa
Na3 citrate 2H2Oa
K2SO4
K2CO3
KCl
CaCl2 2H2O
MgCl2 6H2O

11.61
3.70
6.09
1.03
2.17
8.05
8.98
3.21

Citrate C6 H8 O
3.

Fig. 2. Schematic representation of the rotating disk apparatus.

cium phosphate under controlled hydrodynamics and

temperature. The apparatus is composed of a thermostatic vessel where the solution is contained, temperature
being controlled by a hot water bath and by a hollow
cone containing heated silicone oil. Deposition occurs
on the stainless steel plate attached to the bottom of
the cone. The plate/cone set is allowed to freely rotate
in the solution, the Reynolds number of the system
being controlled by its rotating speed. In the present
work, the rotating speed during deposit formation was
150 rpm (laminar regime, Re = 4.6 104).
Opposed to the constant composition method which
has been more commonly used in crystallization experiments (Koutsoukos et al., 1980; Nancollas & Wu, 2000),
during the present experiments the pH of the solutions
was allowed to decrease freely without any kind of control, as it would occur in real milk heating processes.
The stainless steel samples were attached to the heating cone and then introduced in the foulant solution
contained in the heated vessel. The test solutions (modied SMUF and SMUF at pH 6.80) were heated, at a dened heating rate, to the desired deposition temperature
(45 C). The cone/plate set was kept rotating for 120 min
to allow the formation of a stable deposit on the stainless steel plate. After that time, the set was gently removed from the solution. The plate was detached from
the cone, dried at air and the amount of deposit obtained was weighed. Detailed analyses of the deposits
were made at this point.
The foulant solution was then replaced by distilled
water adjusted to the same pH and temperature of deposition. The set composed by the cone and the fouled
plate was introduced in the water and was rotated at
increasing speeds of 165, 180, 210, 240, 270 and
300 rpm. Each of these rotating experiments were carried out for 5 min. After each experiment, the sample

382

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

was removed, dried and weighed in order to assess the

total amount of deposit detached from the surface.
Particle formation in the bulk can be detected by the
increase in the turbidity of the solution (Andritsos et al.,
2002; Visser, 1999) and by a decrease in the pH value
(Christoersen, Christoersen, & Kibalczyc, 1990). pH
variation during heating was measured (WTW Inolab
pH level 3) and turbidity was followed using a UV/
VIS spectrophotometer (Philips PU8620) at a wavelength of 610 nm, taking one sample for every temperature degree increase.
As soon as the solution became turbid and at the end
of the deposition experiment (after 120 min at constant
temperature), part of the solution was vacuum ltered
and the deposit was examined with scanning electron
microscopy and characterized by X-ray microanalysis
and X-ray diraction (X
Pert Pro PANalytical diractometer with a Cu X-ray tube) to dene their
crystallinity.
Calcium concentration of the dierent solutions at
the beginning of the experiments was measured using a
selective electrode (WTW-D82362 Weitheim).

3. Results and discussion

Abs (610 nm)

As mentioned before, the solutions with and without

citrate presented dierent pH values immediately after
preparation. The experiments performed with SMUF
solution at dierent pH (6.15, 6.30 and 6.80) aimed to
investigate possible pH eects on the deposition process.
The dierence in the pH of the solutions prepared with
or without citrates, keeping all the remaining components constant, has already been described by other
authors, although in a dierent but still exclusively mineral system, who discussed the synergetic role of citrate
ions when raising the pH (Allie & Rodgers, 2003).
Citrates are known to be calcium binders (Andritsos
et al., 2002; Nancollas & Wu, 2000), the main consequence of their presence being the decrease of calcium
free ions in solution. The concentration of free calcium
ions in solution for the dierent solutions analysed is
presented in Table 2.
As can be easily veried in Table 2, the concentration
of calcium ions in solution is similar for all the three
SMUF solutions and much higher for the modied solu-

Table 2
Initial concentration of free calcium in solution
Solutions
Modied SMUF
SMUF (pH 6.15)
SMUF (pH 6.35)
SMUF (pH 6.80)

tion which does not contain citrates. This was the rst
physical observation which seemed to conrm the complexing eect of calcium by the citrates and the fact that
interactions could appear between citrate and all the
other calcium compounds formed in solution. The logarithmic values of the calcium concentration were calculated and are presented in that table but will be used
later on Fig. 9. The concentration of phosphorous is
not presented since it is not inuenced by the presence
of citrates (van der Houwen & Valsami-Jones, 2001).
Bulk precipitation was initiated when supersaturation
occurred as a result of the increase temperature due to
heating. In order to know the temperature at which bulk
precipitation starts, the heating eects on the solutions
were monitored by spectroscopy at 610 nm (Fig. 3).
The initiation of particle formation was detected at different temperatures depending on the solution. A delay
in this starting point for the SMUF solutions can be explained by the fact that citrates removed the available
calcium from solution and consequently supersaturation
according to calcium phosphate was only achieved at
higher temperatures. The modied SMUF solution became turbid at a lower temperature than the others, at
about room temperature. In this situation, all the calcium is consumed to form calcium phosphates. On the
other hand, all the non-modied SMUF solutions
needed higher temperatures to acquire enough supersaturation for precipitation and in those cases, a decrease
in the pH from 6.80 to 6.15 corresponds to an increase
in the temperature at which precipitation starts from
45 to 70 C (Fig. 3). This suggests the existence of an
alternative mechanism with inhibition of nucleation
and/or growth, due to citrate binding onto active growth
sites of the newly formed nuclei. In such a case, growth
of the nuclei is inhibited until there is enough supersaturation of calcium in solution for precipitation to occur.
Some previous studies also found that the presence of
citrate delays the occurrence of crystals and reduces
the crystallization rate which slows down the transformation of these particles into a more stable calcium

Calcium concentration
(mM)

Log (calcium
concentration [M])

4.25
0.75
0.70
0.48

2.38
3.12
3.15
3.30

0.2

modified SMUF

0.18

SMUF pH 6.15

0.16

SMUF pH 6.35

0.14

SMUF pH 6.80

0.12
0.1
0.08
0.06
0.04
0.02
0
0

20

40

T(C)

60

80

100

Fig. 3. Turbidity evolution of the solutions during heating.

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

modified SMUF
SMUF pH 6.80

7
6.8
6.6

beginning of turbidity

pH

6.4

beginning of turbidity

6.2
6
5.8
5.6
5.4
5.2
5
20

25

30

35

40

45

50

T (C)

Fig. 4. pH decrease with heating of modied SMUF and SMUF at pH

6.80.

phosphate form (van der Houwen, Cressey, Cressey, &

Valsami-Jones, 2003).
Fig. 4 shows in more detail the case of modied
SMUF (pH of 6.15) and non-modied SMUF at pH
6.80, where the increase in turbidity is also related to a
decrease in pH. The precipitation of calcium phosphate
from solution is a base uptake process because of the
dissociation of the hydrogen-containing phosphate species present. In a given precipitation system without base
addition, the pH value will decrease during the precipitation reaction. For this reason, the decrease in pH
can be used as a measure of calcium phosphate particle

383

formation in solution. Despite similar changes in turbidity, the decrease in pH is dierent depending on the solution: 5 C above the temperature at which turbidity
starts the pH of the modied SMUF decreased by 0.4
units, while for the same temperature variation a decrease of only 0.1 units was found in SMUF. This variation on pH decrease can also be related to the
formation of dierent calcium phosphate species as different species have dierent alkalinities.
To verify which structures were being formed under
the dierent conditions considered in this work, the
solutions were ltered after reaching an optical density
of 0.2 and the precipitates were analysed by X-ray
microanalysis and observed by scanning electron
microscopy (SEM). All the precipitates were mainly
composed of calcium phosphate, with a very small
amount of magnesium or sodium which is not surprising
since these ions were present in the initial solutions (Fig.
5).
According to the pictures in Figs. 6 and 7, obtained
by scanning electron microscopy (SEM), dierent calcium phosphate structures were formed depending on
the composition and pH of the solution. Structures
formed from SMUF at pH 6.80 (Fig. 6) consisted of
spherical crystals held together in clusters similar to
bunches of grapes, which had already been reported as
characteristic of hydroxyapatite compounds (van

Fig. 5. X-ray microanalysis of the dierent precipitates formed on solution upon heating: (a) modied SMUF, (b) SMUF at pH 6.15, (c) SMUF at
pH 6.30 and (d) SMUF at pH 6.80.

384

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

Fig. 6. Calcium phosphate structures obtained from SMUF at pH 6.80: (a) 5000 amplication and (b) 50,000 amplication.

Fig. 7. Calcium phosphate structures obtained from SMUF at pH 6.15: (a) 5000 amplication and (b) 50,000 amplication.

Kemenade & de Bruyn, 1987; Visser & Jeurnink, 1997).

The structure of the precipitates formed from SMUF at
pH 6.15 was somewhat dierent: although also packed
in a bunch of grape form, the individual spheres were
bigger and showed a more irregular structure (Fig. 7)
which had also been identied as hydroxyapatite in a
non-crystalline form, more precisely in an intermediate
stage between brushite and hydroxyapatite (Ferreira,
Oliveira, & Rocha, 2003). A similar structure, although
not presented here, was found for SMUF at pH 6.30.
The most signicant dierence in structure and morphology was found for the precipitate formed from the
modied SMUF solution, where calcium phosphate
showed a plate-like shape typical of brushite (Fig. 8).
According to the solubility isotherms of calcium phosphate (Fig. 1), the precipitating phase depends on the
relation between the calcium concentration in solution
and the pH. The dierent situations analysed in this
work are presented in Fig. 9, considering the logarithmic
values of calcium concentration in the solution. Calcium
concentrations in the three SMUF solutions (points 2, 3
and 4 in Fig. 9) are much lower than that in the solution
without citrate, as a result of calcium complexation
promoted by the citrates (van der Houwen & ValsamiJones, 2001). The solution could be considered supersaturated according to hydroxyapatite and so the

Fig. 8. Calcium phosphate structures obtained from modied SMUF

with 1500 amplication.

formation of hydroxyapatite precipitates could be

expected. For the solution without citrates, where the
calcium concentration in solution is higher and the
initial pH is lower (point 1 in Fig. 9), the most probable
precipitate was dicalcium phosphate dihydrate or
brushite.

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

Fig. 9. Solubility isotherms for calcium phosphate and the dierent

binomial calcium concentration in solution/pH for the solutions
analysed: (1) modied SMUF, (2) SMUF pH 6.15, (3) SMUF pH
6.30 and (4) SMUF pH 6.80.

Similar results were also found by other authors who

claimed that the presence of citrate in solution was also
responsible for lowering the supersaturation in terms of
brushite (Allie & Rodgers, 2003).
The identication of the structures involved and its
crystallinity can be seen in detail in Fig. 10 containing
the X-ray diraction diagrams of the precipitates. All
the precipitates formed from SMUF showed very similar patterns of poorly crystalline hydroxyapatite, with
no evidence of any other phase being present. The precipitates formed from the solutions at pH of 6.15 (Fig.
10c) and 6.30 (Fig. 10b) showed an amorphous structure
with a small peak in early development, which is characteristic of hydroxyapatite, while the one from the SMUF

385

solution at pH 6.80 (Fig. 10a) showed a more structured

hydroxyapatite compound, although not yet crystalline.
On the other hand, the precipitate formed from modied
SMUF was brushite in a perfect crystalline form (Fig.
10d).
The fact that the pH of the solution has a considerable eect on the type of calcium phosphate structure
formed was conrmed by the results presented before.
The formation of the same calcium phosphate phase in
all three SMUF solutions but in dierent crystallinity
stages leads to the conclusion that dierent pH values
with similar ionic concentration aect the crystallinity
instead of the nature of the chemical compound formed.
The absence of citrate (modied SMUF) showed an
even stronger eect on the precipitation process: the
modied SMUF produced a precipitate composed of
brushite in a totally crystalline phase, whereas for the
same pH the non-modied solution formed an amorphous hydroxyapatite phase.
The relationship between the formation of dierent
structures in the bulk and the build up of calcium phosphate deposits on stainless steel surfaces was also studied. After 120 min of deposition, the deposits formed
on the stainless steel surfaces were analysed by scanning
electron microscopy and X-ray microanalysis. It could
be concluded that the structure of the deposits was
determined by the particles present in the bulk, as can
be checked in Fig. 11a for SMUF solution at a pH of
6.80 and in Fig. 11b for modied SMUF.
The rst type of deposit was composed of an initial
layer of hydroxyapatite aggregates, on top of which
other aggregates with a similar sphere-like structure
were formed, developing a multilayer deposit packed
in a grape-like shape form. The second type of deposit

Fig. 10. X-ray diraction diagram for the dierent calcium phosphate precipitates formed: (a) SMUF pH 6.80, (b) SMUF pH 6.30, (c) SMUF pH
6.15 and (d) modied SMUF.

386

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

Fig. 11. Deposits formed on 2R stainless steel surfaces after 120 min of deposition: (a) SMUF pH 6.80 and (b) modied SMUF.

Table 3
Mass of deposit formed on 2R stainless steel surfaces after 120 min
deposition experiments and percentage of deposit removal in cleaning
experiments (r is the standard deviation)
Solutions

Mass of
deposit (g/m2)

Percentage
of removal (%)

Modied SMUF (without citrate)

SMUF (pH 6.80) (with citrate)

5.5 (r 0.2)
2.5 (r 0.1)

78.4 (r 0.9)
76.1 (r 0.2)

(Fig. 11b) showed a less dened rst layer where the

plate-like structures seem to be laid on. The removal
experiments suggested that they were in fact adhered
to the surface.
The amount of deposit formed in each case (after
120 min deposition) and the amount of mass deposit removed after the removal experiment cycle are presented
in Table 3. Under the same deposition conditions, the
mass of deposit formed was the double for the brushite
case (without citrate). Although opposed to what has
been reported earlier by Andritsos et al. (2002), this
could be expected since the structures formed in the
bulk, the ones responsible for the build up of the deposit, were much larger in the brushite case. It was interesting to nd that under the same hydrodynamic
conditions, a similar percentage of mass was removed
from the surface, independently of the deposit morphology and composition.

4. Conclusions
In this work, the eect of citrates on the precipitation
of calcium phosphate from an aqueous solution which
simulates the mineral composition of milk (SMUF)
was evaluated. Three main parameters were aected by
the presence or absence of citrates: (1) the pH of the
solution before precipitation was lower in the absence
of citrates; (2) the calcium phosphate phase that

precipitated when heating the solution changed from

hydroxyapatite in the presence of citrates to brushite
in the absence of citrates and (3) the deposits that build
up on stainless steel surfaces in each case had dierent
morphology and total mass but showed similar resistance to detachment when submitted to similar hydrodynamic forces. This last conclusion is especially
important when choosing the cleaning strategies to
apply in fouled heat exchangers, since it means that
although a greater percentage of the brushite deposit
(absence of citrate) can be removed from the surface,
the remaining deposit mass is higher than in the case
of hydroxyapatite (presence of citrate).

Acknowledgments
The authors gratefully acknowledge the nancial support of the MODSTEEL Project (The European Commission, DG Research, Growth Programme, Contract
no. G5RD-CT-1999-00066) and the SIMUMILK Project (FCT, Portuguese Science Foundation, POCTI/
QUE/47654/2002).

Appendix A. Nomenclature and units

T
Re

temperature (C)
Reynolds number (dimensionless)
2

Re X tx h5  104 i for laminar regime

X
plate dimension (m)
x
angular velocity (rad/s)
m
kinematic viscosity of the uid (m2/s)
SMUF simulated milk ultraltrate
HAP hydroxyapatite
DCPD dicalcium phosphate dihydrate or brushite
[CaHPO4 2H2O]
OCP
octacalcium phosphate [Ca4H(PO4)3 2.5H2O]

R. Rosmaninho, L.F. Melo / Journal of Food Engineering 73 (2006) 379387

TCP
ACP

tricalcium phosphate [Ca3(PO4)2]

amorphous calcium phosphate

References
Abbona, F., & Franchiniangela, M. (1990). Crystallization of calcium
and magnesium phosphates from solutions of low concentration.
Journal of Crystal Growth, 104(3), 661671.
Allie, S., & Rodgers, A. (2003). Eects of calcium carbonate,
magnesium oxide and sodium citrate bicarbonate health supplements on the urinary risk factors for kidney stone formation.
Clinical Chemistry and Laboratory Medicine, 41(1), 3945.
Andritsos, N., Yiantsios, S. G., & Karabelas, A. J. (2002). Calcium
phosphate scale formation from simulated milk ultraltrate solutions. Food and Bioproducts Processing, 80(C4), 223230.
Christoersen, M. R., Christoersen, J., & Kibalczyc, W. (1990).
Apparent solubilities of 2 amorphous calcium phosphates and of
octacalcium phosphate in the temperature-range 3042 C. Journal
of Crystal Growth, 106(23), 349354.
Ferreira, A., Oliveira, C., & Rocha, F. (2003). The dierent phases in
the precipitation of dicalcium phosphate dihydrate. Journal of
Crystal Growth, 252(4), 599611.
House, W. A. (1999). The physico-chemical conditions for the
precipitation of phosphate with calcium. Environmental Technology, 20(7), 727733.
Jenness, R., & Koops, J. (1962). Preparation and properties of a salt
solution which simulates milk ultraltrate. The Netherlands Milk
and Dairy Journal, 16(3), 153164.
Jeurnink, T. J. M., Walstra, P., & deKruif, C. G. (1996). Mechanisms
of fouling in dairy processing. The Netherlands Milk and Dairy
Journal, 50(3), 407426.
Koutsoukos, P., Amjad, Z., Tomson, M. B., & Nancollas, G. H.
(1980). Crystallization of calcium phosphates - constant composi-

387

tion study. Journal of the American Chemical Society, 102(5),

15531557.
Liu, Y., Sethuraman, G., Wu, W. J., Nancollas, G. H., & Grynpas, M.
(1997). The crystallization of uorapatite in the presence of
hydroxyapatite seeds and of hydroxyapatite in the presence of
uorapatite seeds. Journal of Colloid and Interface Science, 186(1),
102109.
Milev, A., Kannangara, G. S. K., & Ben-Nissan, B. (2003). Morphological stability of hydroxyapatite precursor. Materials Letters,
57(13-14), 19601965.
Nancollas, G. H., & Wu, W. J. (2000). Biomineralization mechanisms:
A kinetics and interfacial energy approach. Journal of Crystal
Growth, 211(1-4), 137142.
Sharma, V. K., Johnsson, M., Sallis, J. D., & Nancollas, G. H. (1992).
Inuence of citrate and phosphocitrate on the crystallization of
octacalcium phosphate. Langmuir, 8(2), 676679.
van der Houwen, J. A. M., Cressey, G., Cressey, B. A., & ValsamiJones, E. (2003). The eect of organic ligands on the crystallinity of
calcium phosphate. Journal of Crystal Growth, 249(3-4), 572583.
van der Houwen, J. A. M., & Valsami-Jones, E. (2001). The
application of calcium phosphate precipitation chemistry to
phosphorus recovery: The inuence of organic ligands. Environmental Technology, 22(11), 13251335.
van Kemenade, M. J. J. M., & de Bruyn, P. L. (1987). A kinetic study
of precipitation from supersaturated calcium-phosphate solutions.
Journal of Colloid and Interface Science, 118(2), 564585.
Vereecke, G., & Lemaitre, J. (1990). Calculation of the solubility
diagrams in the system Ca(OH)2H3PO4KOHHNO3CO2H2O.
Journal of Crystal Growth, 104(4), 820832.
Visser, J. (1999). Reducing fouling of heat exchangers in the dairy
industry by process optimization. In D. I. Wilson, P. J. Fryer, & A.
P. M. Hasting (Eds.), Proceedings of fouling and cleaning in food
processing
98. EU.
Visser, J., & Jeurnink, T. J. M. (1997). Fouling of heat exchangers in
the dairy industry. Experimental Thermal and Fluid Science, 14(4),
407424.