Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 213–216
Communication
Silica scale inhibition by polyaminoamide STARBURST
®
dendrimers
Eleftheria Neofotistou, Konstantinos D. Demadis
∗
Department of Chemistry, University of Crete, Heraklion, Crete, GR-71409, Greece
Received 1 December 2003; accepted 23 April 2004
Abstract
This paper reports the inhibition efficiency of a family of polyaminoamide (PAMAM) STARBURST
®
dendrimers in colloidal SiO
2
growth.
PAMAMs of various generations (0.5, 1.5, 2.5 with –COOH termini, and 1, and 2 with –NH
2
termini) were tested and compared to control
samples. Superiority of the dendrimer inhibitors with –NH
2
termini (maintaining ∼380 ppm soluble SiO
2
after 12 h) versus those with –COOH
termini (maintaining ∼180 ppm soluble SiO
2
after 12 h) was discovered in solutions containing 500 ppm initial SiO
2
. These inhibitors present
potential for water treatment applications.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Polyaminoamide; Silica scale inhibition; STARBURST
®
dendrimer; Water treatment; Deposit
Dendrimers are well-defined globular macromolecules
constructed around a core unit [1]. Tomalia pioneered the
synthesis of polyaminoamide (PAMAM) dendrimers, known
as “STARBURST
®
polymers”, Fig. 1 [2]. Their main struc-
tural feature is the growth of the dendrimer branches around
a central core (in this case an ethylenediamine) via amide
chemical linkages. The dendrimer generation number indi-
cates its degree of growth and branching. More specifically,
PAMAMs of generations 0.5, 1.5, 2.5 possess –COOH ter-
mini, and those of generations 1 and 2 have –NH
2
termini.
Fundamental studies, as well as a plethora of applications
are at the epicenter of interest [3]. Our research efforts are
currently focused on developing new chemistries for scale
growth control, as it relates to chemical water treatment
[4]. We have studied a novel application of STARBURST
®
dendrimers as silica (SiO
2
) scale growth inhibitors in process
industrial waters, and we describe herein our findings.
Silicate ion polymerizes via a condensation polymeriza-
tion mechanism, at appropriate pH regions [5]. When it oc-
curs in process waters used for cooling purposes, the result-
ing silica precipitates form a hard and tenacious scale on
Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.colsurfa.2004.04.067.
∗
Corresponding author. Tel.: +30-2810-393651;
fax: +30-2810-393601.
E-mail address: demadis@chemistry.uoc.gr (K.D. Demadis).
critical industrial equipment, such as heat exchangers, trans-
fer pipes, etc. Silica removal by dissolution is a challenge [6]
and the usual approaches to control it are avoiding supersatu-
ration (leading to water wastage) or pre-treatment (with high
equipment costs). Research on chemical inhibitors for SiO
2
is ongoing, but actual applications of inhibition chemistries
in the field are rather limited.
Various generations of STARBURST
®
dendrimers were
screened by a SiO
2
supersaturation test.
1
Test solutions
of 500 ppm silicate (as SiO
2
) were utilized in this study
2
1
Screening tests: Control. A 100 mL volume of 500 ppm SiO
2
stock
solution in the form of Na
2
SiO
3
·5H
2
O is placed in a polyethylene con-
tainer charged with a teflon-covered magnetic stir bar. The pH of this
solution is initially ∼11.8 and adjusted to 7.00 ± 0.1 by addition of HCl
(the change in the resulting volume is negligible). The beaker is then
covered and set aside without stirring. The solution is checked for solu-
ble SiO
2
by the silicomolybdate spectrophotometric method every 2 h for
the first 12 h or after 24, 48, 72 h time intervals after the pH reduction.
Inhibitor test. The procedure above is followed except that before pH
adjustment 400 L of inhibitor a 10,000 ppm stock solution is added to
achieve a final inhibitor concentration of 40 ppm. Sampling and timing
are the same as the control, except that samples are first filtered through
a 0.45 micron syringe filter before testing for soluble SiO
2
. Most of the
results were reproduced several times with excellent reproducibility, es-
pecially those with PAMAM-1 and -2 as inhibitors.
2
These are considered to be “high stress” conditions with respect to
SiO
2
supersaturation. Most untreated industrial cooling systems operate
at <200 ppm SiO
2
. Use of these “high stress” conditions is necessary in
order to differentiate between inhibitor efficiencies.
0927-7757/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.04.067