APPLICATION
❙ Z. Amjad
Role of Heat Treatment
on the Performance of Polymers
as Iron Oxide Dispersants
The influence of heat treatment on the performance of various
polymers as iron oxide dispersants in an aqueous system has
been investigated. The polymers evaluated include: homo-poly-
mers of acrylic acid, methacrylic acid, maleic acid; co-polymer of,
acrylic acid:2-acrylamido-2-methylpropane sulfonic acid; ter-
polymers of acrylic acid:2-acrylamido-2-methyl propane sulfonic
acid:sulfonated styrene, and acrylic acid:2-acrylamido-2-methyl-
propane sulfonic acid:t-butylacrylamide. It has been found that
all polymers lose performance to a varying degree when ex-
posed to thermal treatment (150 °C, 200 °C, 20 hr). The perfor-
mance data also suggest that sulfonated styrene containing ter-
polymer is a better iron oxide dispersant than the ter-polymer
containing 2-acrylamido-2-methylpropane sulfonic acid and ter-
tiary butylacrylamide. In the case of co-polymer of acrylic acid:2-
acrylamido-2-methylpropane sulfonic acid, the thermal treat-
ment exhibits strong negative influence on the dispersancy
power of the polymer. The results have been explained in terms
of loss of 2-acrylamido-2-methylpropane sulfonic acid and t-bu-
tylacrylamide in the co- and ter-polymers, as determined by FT-
IR and NMR methods, leading to the formation of poly(acrylic
acid).
Key words: Polymer, dispersion, thermal stability
Einfluss einer Wärmebehandlung auf die Leistungsfähigkeit
von Polymeren als Eisenoxid-Dispergiermittel. Der Einfluss ei-
ner Wärmebehandlung wurde auf die Leistungsfähigkeit ver-
schiedener Polymere als Eisenoxid-Dispergiermittel in wässrigen
Systemen untersucht. Bewertet wurden folgende Polymere:
Homopolymere von Acrylsäure, Methacrylsäure, Maleinsäure;
Copolymere von Acrylsäure:2-Acrylamido-2-methylpropansul-
fonsäure; Terpolymere von Acrylsäure:2-Acrylamido-2-methyl-
propansulfonsäure:sulfoniertes Styrol und Acrylsäure:2-Acryl-
amido-2-methylpropansulfonsäure:t-Butylacrylamid. Es wurde
gefunden, dass alle Polymere an Leistungsfähigkeit mit un-
terschiedlichem Ausmaß einbüßen, wenn sie einer thermischen
Behandlung (150 °C, 200 °C, 20 h) ausgesetzt werden. Die Leis-
tungswerte zeigen, dass sulfoniertes Styrol mit Terpolymer ein
besseres Eisenoxid-Dispergiermittel ist als ein Terpolymer mit
2-Acrylamido-2-methylpropansulfonsäure und tertiäres Butyl-
acrylamid. Im Fall des Copolymers von Acrylsäure:2-Acrylamido-
2-methylpropansulfonsäure zeigt die thermische Behandlung ei-
nen starken negativen Einfluss auf die Dispergierfähigkeit des
Polymers. Die Ergebnisse sind erklärbar durch einen Verlust an
2-Acrylamido-2-methylpropansulfonsäure und t-Butylacrylamid
bei den Co- und Terpolymeren, was zu einer Ausbildung von
Polyacrylsäure führt und mittels FT-IR- und NMR-Methoden be-
stimmt wurde.
Stichwörter: Polymer, Dispersion, thermische Stabilität
242  Carl Hanser Publisher, Munich
1 Introduction
Feed water available for domestic and industrial uses is gen-
erally contaminated with various forms of dissolved ions
(i. e., calcium, magnesium, carbonate, sulfate, etc.), colloi-
dal, and suspended matter (i. e., clay, silt, organic debris, cor-
rosion products, etc.). The type, size, and concentration of
suspended particles affect their behavior in water systems.
In addition, metal ions (i. e., Cu, Mn, Fe) present in feed
water may get hydrolyzed and/or oxidized under conditions
typically encountered in domestic and industrial systems.
Maintaining this hydrolyzed and/or oxidized metal ions in
soluble and in dispersed forms can prevent the build-up of
unwanted deposits on various substrates.
Although feed waters contain a variety of suspended
matter, iron-based foulants (e. g., Fe2O3, Fe3O4, Fe(OH)3,
FePO4) are generally considered to be one of the most chal-
lenging problems. The four major approaches to control
iron oxide deposits are: (a) removing iron oxides (corrosion
products) from the systems (filtration), (b) inhibiting corro-
sion at its source (this is achieved by the use of corrosion in-
hibitors), (c) stabilizing Fe(II) and Fe(III) ions in the feed
water (involves the use of iron selective chelants), and (d)
treating the feed or re-circulating water with iron oxide dis-
persant(s) to minimize iron oxide deposition within the sys-
tem. The use of dispersant is generally considered to be the
most economical method.
The suspended particles typically encountered in indus-
trial water applications generally carry a slight negative
charge. Therefore, anionic polymers are normally the most
efficient dispersants because these anionic polymers in-
crease the negative surface charge and keep particles in sus-
pension. Cationic polymers can be used as dispersants but
this requires relatively high polymer concentrations in order
to first neutralize the negative surface charges and then to
transfer cationic charge to particles for efficient dispersion.
Suspension of clays, metal oxides, pigments, ceramic
materials, and other insoluble inorganic particulate solids
in aqueous systems through the use of small quantities of
synthetic polymers, polyphosphates and other polyelectro-
lytes has become an increasingly important area of study
with high technological relevance [1 – 4]. Dubin [5] in his in-
vestigation on the evaluation of polyphosphates, organopho-
sphonates, poly(acrylic acid), P-AA; poly(maleic acid), P-MA;
and co-polymer of acrylic acid:maleic acid (P-AA:MA) as dis-
persants for iron oxide showed that acrylic acid and maleic
acid based polymers performed better than polyphosphates
and organophosphonates. The effectiveness of polymers as
dispersants for clay and iron oxide has been the subject of
numerous investigations. It has been reported that polymers
containing different functional groups i. e., carboxyl, amino,
sulfonic, amido, etc., are effective dispersants [5 – 7]. In addi-
tion, it has also been shown that polymer molecular weight
plays an important role in dispersing suspended matter in
Tenside Surf. Det. 43 (2006) 5
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
aqueous systems. Recently, the influence of polymer archi-
tecture in dispersing many ceramics has been the subject
of numerous investigations. Results of these studies have
shown that acrylic copolymers containing acrylic acid group
and other monomers, such as alkyl ester group, possess
properties different from those of P-AA [8 – 10].
Thermal degradation of polymers is a well studied area.
However, there is little information available of real value to
industrial technologists concerned with using low molecular
weight polymers. Polymers used in high temperature appli-
cations should be able to sustain high temperature and pres-
sure environments normally associated with boiler and ther-
mal desalination operations. McGaugh and Kottle [11]
studied the thermal degradation of poly(acrylic acid) and la-
ter the thermal degradation of an acrylic acid-ethylene co-
polymer. They used infrared and mass spectrographic analy-
sis to examine the degradation processes that occurred in
the temperature regions 25 – 150 °C, 150 – 275 °C, 275 to
350 °C and above 350 °C. Their results suggest that in air
(min heating) dry poly(acrylic acid) decomposes by forming
an anhydride, probably a six-membered glutaric anhydride-
type structure at temperature up to 150 °C. At 350 °C there
is drastic unmeasurable change and strong unsaturation ab-
sorption. Mass spectrographic analysis showed that carbon
dioxide was the major volatile product at 350 °C.
Denman and Salutsky [12] briefly examined the thermal
stability of a sodium poly(methacrylate) and a sodium poly-
(acrylate). Under dry conditions they found no change to
316 °C after one (1) hour but some charring at 371 °C. Mas-
ler [13] investigated the thermal stability of several homo-
polymers used in the boiler. It was demonstrated that under
the experimental conditions employed (pH 10.5, 250 °C,
18 hr] that P-AA, P-MA; and poly(methacrylic acid), P-MAA
all underwent some degradation. In terms of molecular
weight loss, P-MAA lost slightly less molecular weight than
P-AA which lost considerably less than P-MA. Additionally,
P-AA and P-MAA had minimal performance changes
whereas P-MA displayed a substantial loss in performance.
McGaugh and Kottle [14] in their study on the polymer
thermal stability showed that P-AA forms an intramolecular
anhydride at temperatures below 150 °C. At higher tempera-
tures, this anhydride appears as an intermediate in the de-
carboxylation of P-AA. Gurkaynak et al. [15] performed very
short degradation tests on a 6000 MW (molecular weight) P-
AA at high temperature and different pH levels. Results of
their study show that rate of decarboxylation depends upon
various parameters i. e., solution pH, ionic strength, and
temperature. Hetper et al. [16] investigated the thermal be-
haviour of sodium, calcium, and magnesium polyacrylates.
They found that the main decomposition of the calcium
and magnesium salts occurs in the temperature range
450 – 490 °C. It was suggested that the thermal degradation
of the metal polyacrylates proceeds via side chain and main
chain scission, without depolymerization. The thermal de-
gradation of calcium and magnesium salts of P-AA has been
recently studied by McNiell and Sadeghi [17]. Results of
their study show some similarities to the behaviour of the
alkali metal salts of P-AA and to that of the alkaline earth
metal salts of P-MAA.
During the last two decades, the influence of polymers
as precipitation inhibitors for scale forming salts i. e., cal-
cium phosphate, calcium carbonate, calcium sulfate, bar-
ium sulfate, calcium fluoride, calcium phosphonate, etc.,
has been the subject of numerous investigations [18 – 22].
However, the impact of thermal stability of polymers on
the performance of polymers as scale inhibitors and as dis-
persants for particulate matter especially iron oxide has
Tenside Surf. Det. 43 (2006) 5
been mostly overlooked. In the present paper, we report
on the results of investigations conducted to gain informa-
tion about the impact of thermal treatment on the perfor-
mance of a variety of polymers used as scale inhibitors
and dispersants in high temperature applications. The poly-
mers we have selected include: a) homo-polymers i. e.,
poly(acrylic acids), P-1, P-2; poly(methacrylic acid), P-3;
poly(maleic acid), P-4; b) co-polymer i. e., poly(acrylic acid :
2-acrylamido-2-methylpropane sulfonic acid), P-5; and c)
ter-polymers i. e., poly(acrylic acid : 2-acrylamido-2-methyl-
propane sulfonic acid : sulfonated styrene), P-6; poly(acrylic
acid : 2-acrylamido-2-methylpropane sulfonic acid : tertiary
butyl acrylamide), P-7; Poly(acrylic acid : methacrylic acid :
tertiary butyl acrylamide, P-8. In addition, an optical micro-
scope was used to study the influence of dispersants on
iron oxide particle size distribution.
2 Experimental
2.1 Materials
Grade A glassware and reagent grade chemicals were used.
The iron oxide (Fe2O3,) used in this investigation was ob-
tained from Fisher Scientific Co. It was characterized as he-
matite by x-ray diffraction (JCPDS phase SS664). The parti-
cle size distribution (with majority of particles in the 50 to
150 micron range) was obtained using a Beckman Coulter
Counter Model LS320. The polymeric materials used as dis-
persants were selected from commercial and experimental
materials and are listed in Table 1. All dispersant solutions
were prepared on a dry weight basis. The desired concentra-
tions were obtained by dilution.
2.2 Thermal treatment of dispersant
A solution of polymer was prepared containing 10 % poly-
mer (as active solids) at pH 10.5 using sodium hydroxide
to neutralize the polymer. Sodium sulfite was used as an
oxygen scavenger. A known amount of polymer solution
was retained for characterization and performance testing.
The balance was charged to a stainless steel tube. The
headspace was purged with nitrogen followed by tighten-
ing the fittings. The tube was then placed in the oven
maintained at the required temperature (either at 150 °C
or 200 °C). At known times tubes were removed from the
oven, cooled to room temperature, and solution was trans-
ferred to vials for polymer characterization and perform-
ance testing.
2.3 Polymer characterization
The molecular weights of polymers were determined accord-
ing to the method described previously [13]. Nuclear mag-
netic resonance (NMR) spectra of polymers before and after
thermal treatment were obtained on a Brubaker AV-500
NMR spectrometer. Attenuated total reflectance infra-red
(FT-IR) spectra of all polymers, neutralized to pH 10 with
NaOH solution were acquired as films on a Nicolet Magna
560 Fourier Transform Infrared (FT-IR) spectrometer.
2.4 Iron oxide particle characterization
At the end of experiments few drops of iron oxide suspen-
sion in the presence and absence of polymers were removed
for particle size characterization by Leica Mz16 stereo-optical
microscope.
243
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
2.5 Iron oxide dispersancy
A known amount (0.12 g) of iron oxide was added to syn-
thetic water (600 mL) containing a known amount of poly-
mer (dispersant) solution adjusted to pH 8 in a 800 mL bea-
ker. The synthetic water used in dispersancy test was made
by mixing standard solutions of calcium chloride, magne-
sium chloride, sodium sulfate, sodium bicarbonate, and so-
dium chloride. The synthetic water has the following com-
position: 100 mg/L Ca, 30 mg/L Mg, 314 mg/L Na,
571 mg/L Cl, 200 mg/L SO4 and 60 mg/L HCO3. The pH
of the synthetic water was adjusted to 8.0 with dilute NaOH
and or HCl solutions.
In a typical test, six experiments were run simulta-
neously using a gang-stirrer. The gang-stirrer was set to
110 rpm (revolutions per minute) speed. At known time in-
tervals transmittance readings (%T) were taken with a
Brinkmann PC/100 colorimeter with 420 nm filter. The ab-
sorbance of several filtered (0.22 micron) suspensions with
low to high %T readings was measured at 420 nm. It was
found that absorbance contribution due to dissolved species
was insignificant (< 3 %). Polymer performance as percent
Table 1 Polymers tested
244
iron oxide dispersed (%D) was calculated, after making cor-
rection for the %T reading obtained in the absence of poly-
mer (90 % T), from %T readings (%D = 100 – 1.11 %T) mea-
sured at 3 hr as the amount of iron oxide dispersed. The
data presented in this study had good reproducibility (± 5 %
or better). The performance of the polymer was determined
by comparing the %D values of the slurries containing poly-
mer against control (no polymer). Greater dispersancy was
therefore indicated by higher %D value.
3 Results and Discussion
3.1 Dispersant performance
A series of experiments were conducted to evaluate the per-
formance of polymers as iron oxide dispersants both with
and without heat treatment. Table 1 shows the structures of
polymers evaluated in the present study. The experiments
were designed to evaluate the performance of polymer as a
function of dosage, dispersant architecture, the impact of
heat treatment, and calcium ion compatibility.
Tenside Surf. Det. 43 (2006) 5
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
3.1.1 Effect of dispersant dosage
Figure 1 presents dispersancy data as a function of disper-
sant concentration for three polymers namely homo-poly-
mers of acrylic acid of varying molecular weight (MW), P-1,
MW 2000; P-2, MW 10000 and a co-polymer of acrylic
acid:2-acrylamido-2-methylpropane sulfonic acid, P-5, MW
< 15 000. It can be seen that polymer concentration strongly
affects the performance of the polymer as iron oxide disper-
sant. For example, at a 0.25 ppm polymer concentration P-1
exhibits poor performance (< 25 %D). However, as the poly-
mer concentration is increased by a factor of two (i. e., from
0.25 to 0.50 ppm), polymer performance is significantly im-
proved and maximum dispersancy is obtained at 1.0 ppm
concentration. As illustrated in Figure 1 further increase in
polymer concentration (i. e., from 1.0 to 1.5 ppm) does not
exhibit any significant improvement in dispersancy value.
It is worth noting that under similar experimental condi-
tions polymer performance as iron oxide dispersant de-
creases with increasing molecular weight. For example, %D
values obtained in the presence of 1.0 ppm of P-1 (MW
2000) and P-2 (MW 10000) are 41 % and 11 %, respectively.
The observed decrease in polymer performance with in-
creasing MW is consistent with earlier studies on the disper-
sancy of hydroxyapatite by polymers [23].
The %D data as a function of co-polymer (P-5) concentra-
tion is presented in Figure 1. It is evident from Figure 1 that
P-5 is more effective in dispersing iron oxide than P-1 thus
suggesting the presence of sulfonic acid group in P-5 exhib-
Tenside Surf. Det. 43 (2006) 5
its marked influence in imparting more negative charge on
iron oxide particles. The improved performance of P-5 over
P-1 may be attributed to the presence of two functional
groups (i. e., carboxyl and sulfonic acid) compared to only
one functional group (i. e., carboxyl) present in P-1.
3.1.2 Effect of heat treatment
Figure 2 presents performance data for several polymers at
1.0 ppm polymer concentration under standard test condi-
tions. As shown in Figure 2, the homo-polymers (i. e., P-1,
P-3, and P-4) before heat treatment provide relatively poor
(< 50 %) iron oxide dispersion. Furthermore, the iron oxide
dispersancy values for both heat treated and non-heat trea-
ted homo-polymers are very similar. This indicates that heat
stress (exposure of aqueous solutions of these homo-poly-
mers to 200 °C, 20 hr) has a negligible detrimental effect
(< 10 % loss in %D) on the dispersing power of the poly-
mers. The data presented in Figure 2 suggest that polymers
containing only carboxyl group do not significantly decarb-
oxylate under the test conditions.
Masler [13] in his investigation on the effect of thermal
treatment (250 °C, 18 hr, pH 10.5) of several homo-polymers
reported that P-MAA lost slightly less molecular weight than
P-AA which lost considerably less molecular weight than P-
MA. In terms of P-AA decarboxylated less than P-MAA
which decarboxylated less than P-MAA. In addition, it was
reported that P-MA lost ∼ 40 % activity as a calcium carbo-
Figure 1 Effect of polymer dosage on iron
oxide dispersancy by homo- and co-polymer
Figure 2 Effect of heat treatment on the
performance of homo-, co-, and ter-polymers
as iron oxide dispersants
245
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
nate inhibitor after heat treatment at 250 °C for 18 hr. It is
interesting to note that under similar experimental condi-
tions P-AA and P-MAA lost only ∼ 5 – 8 % inhibitory activity
thus suggesting that carboxyl content in the polymer plays
an important role in inhibiting the precipitation of calcium
carbonate. Gurkaynak et al. [14] investigated the high tem-
perature degradation of P-AA in aqueous solution as a func-
tion of pH, ionic strength, and temperature. Results of their
study show that rate of decarboxylation of P-AA decreases
with increasing pH (i.e, COO– is relatively more stable than
COOH) and the rate of decarboxylation increases rapidly as
the temperature is increased from 250 °C to 350 °C. The dis-
persancy data presented in Figure 2 suggest that there was
no significant loss of dispersancy or carboxyl content under
the experimental conditions employed in the present condi-
tions (200 °C, 20 hr, pH 10.5). The insignificant loss in dis-
persancy or decarboxylation as observed in the present in-
vestigation is thus consistent with previously reported
studies on the thermal stability of P-AA in alkaline pH [14].
Comparative dispersion data on several co- and ter-poly-
mers are presented in Figure 2. As illustrated, both the co-
and ter-polymers in the absence of thermal stress exhibit ex-
cellent (> 80 %) iron oxide dispersion. However, when these
co-and ter-polymers are exposed to heat stress (200 °C,
246
20 hr), the iron oxide dispersancy decreases drastically (by a
factor 4). For example, % iron oxide dispersancy values ob-
tained for co-polymer (P-5) before and after heat treatment
were 84 % and 14 %, respectively. It is worth noting that
the performance of heat treated co-polymer is similar to that
obtained for poly(acrylic acid), P-2 (Fig. 2), of similar mole-
cular weight (∼ 10 000). The observed marked decrease in P-
5 performance clearly indicates that 2-acrylamido-2-methyl-
propane sulfonic acid (SA) present in P-5 underwent serious
degradation upon exposure to heat treatment thus leading to
the formation of poly(acrylic acid).
Iron oxide dispersancy data for ter-polymers (i. e., P-6, P-
7, and P-8) are also illustrated in Figure 2. As shown, all of
the three ter-polymers in the absence of heat treatment show
excellent (> 80 %) dispesancy power. It is evident from Fig-
ure 2 that P-6, P-7 and P-8 upon heat treatment (200 °C,
20 hr) lost significant dispersancy ability. For example, %D
values obtained for P-6, P-7, and P-8 before heat treatment
were 89 %, 86 % and 82 %, respectively compared to 32 %,
20 %, and 15 %, respectively obtained for heat treated ter-
polymers. As shown in Table 1, the structural difference be-
tween P-6 and P-7 is due to the presence of a third mono-
mer i. e., sulfonated styrene, SS, in P-6 versus tertiary butyl
acrylamide, t-BuAm, in P-7. Similarly, in P-7, SA has been
Figure 3 Plots of molecular weight loss due to heat
treatment for various polymers
Figure 4 FT-IR spectra of
poly(acrylic acid) before and
after heat treatment at 200 °C
for 20 hr
Tenside Surf. Det. 43 (2006) 5
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants

replaced with methacrylic acid to yield P-8. From the data
presented in Figure 3 it is clear that upon subjecting the
ter-polymers to heat treatment, P-7 and P-8 lost more inhibi-
tory power compared to P-6. The observed decrease in per-
formance between these two-ter-polymers suggests that SS
is thermally more stable than the t-BuAm and SA.
3.1.3 Effect of temperature
The influence of temperature on the thermal stability of
polymers was also investigated at both 150 °C and 200 °C.
The performance data presented in Figure 2 illustrate excel-
lent thermal stability for the poly(methacrylic acid), P-3, and
two poly(acrylic acid), P-1 and P-2 evaluated at both 150 °C
and 200 °C. The baseline performance (without heat treat-
ment) for the two acrylic acid-based ter-polymers is better
than for the homo-polymers tested.
Figure 2 also shows a comparison of the ter-polymers
that have the same baseline performance before heat treat-
ment. However, as the polymers are exposed to 150 °C and
200 °C, a marked decrease in polymer performance is ob-
served. It should be noted that compared to P-6, P-7 lost
more dispersancy power at both temperatures. The observed
difference in ter-polymer performance suggests better stabi-
lity of SS over t-BuAm.
3.2 Polymer characterization
3.2.1 Molecular weight
It is well known that molecular weight of a polymer has pro-
found effects on its performance in domestic, biological, and
industrial applications. For example, a low molecular weight
(2000 to 10 000) polymers are effective precipitation inhibi-

Figure 5 FT-IR spectra of co-

polymer (P-5) before and after
heat treatment at 200 °C for
20 hr

Figure 6 FT-IR spectra of ter-

polymer (P-7) before and after
heat treatment at 200 °C for
20 hr

Tenside Surf. Det. 43 (2006) 5 247

Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
tors and dispersing agents for particulate matter whereas
high (> 100,000) molecular weight polymers are poor preci-
pitation inhibitors but may be effective flocculants.
All polymers (synthetic and natural) degrade as a result of
exposure to elevated temperature and pressure. The extent
of degradation depends upon several factors including tem-
perature, duration of heat treatment, and polymer architec-
ture. The polymers used in the present study lost molecular
weight as a result of their thermal degradation. Figure 3 de-
picts the “% molecular weight loss” for homo-, co-, and ter-
polymers. The data show that there is small loss of molecu-
lar weight for homo-polymers (i. e., P-1, P-3) after heating at
200 °C. Figure 3 also shows that ter-polymers are degraded
to a lesser extent than P-5 copolymer. For example, the mo-
lecular weight loss obtained for ter-polymers was ∼ 11 %
compared to 22 % loss in the case of co-polymer. As dis-
cussed earlier the loss in co- and ter-polymers performance
as a result of heat treatment is far greater (60 to 80 %) than
the observed (10 to 20 %) loss in molecular weight. This sug-
gests that the decrease in polymer performance as an iron
oxide dispersant is due to degradation of the functional
group(s) rather than the cleavage of the polymer backbone.
3.2.2 FT-IR spectroscopy
Before and after thermal treatment FT-IR spectra of P-1, P-5,
and P-7 are shown in
248
Figures 4, 5, and 6, respectively. Figure 7 shows the FT-IR
spectra for P-6 before and as well as after 20 hr of heat treat-
ment at 200 °C. In all cases, polyacrylic carboxylate (Na) salt,
which is near 1,565 cm–1 shifted to a 7 – 8 cm–1 lower fre-
quency after heat treatment. The reason(s) for this is not
fully understood, but may reflect a change in pH caused by
the heat treatment.
For those samples containing sulfonic acid group (i. e.,
Figures 5, 6, and 7), the amide carbonyl band near
1,655 cm–1 diminishes and eventually disappears during
heat treatment, as the amide functionality is oxidized. As
the amide carbonyl diminishes, a complementary carboxy-
late salt band near 1,565 cm–1 grows; this band is indistin-
guishable from the carboxylate salt band observed in poly-
acrylate salt type products (i. e., P-1). As the sulfonic acid
component is degraded, the primary sulfonate salt asym-
metric SO3 stretch band near 1,195 cm–1 shifts to an ap-
proximately 15 cm–1 higher frequency. The position of
asymmetric SO3 stretch band near 1,047 cm–1 is essentially
unchanged. However, the relative intensity of this band is
somewhat less in heat-treated samples than in the untreated
samples. The spectra in Figure 7 indicate that the majority
of the thermal degradation occurred after only 4 hr. Further-
more, the greater heat stability of P-6 vs. P-7 is evident by
comparing the spectra in Figures 7 and 6, respectively. It
should be pointed out that observations made in FT-IR
investigation on polymer samples regarding structural
Figure 7 FT-IR spectra of ter-
polymer (P-6) before and after
heat treatment at 200 °C for
4 hr and 20 hr
Figure 8 Calcium ion compatibility of homo-,
co-, and ter-polymers before and after heat
treatment at 200 °C for 20 hr
Tenside Surf. Det. 43 (2006) 5
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants
changes during heat treatment agree well with NMR charac-
terization data obtained for polymer samples before and
after heat treatment.
3.3 Calcium ion compatibility
It has been reported that a polymer's ability to complex
hardness ions is affected by polymer molecular weight [24].
Higher molecular weight polymers typically exhibit better
complexing ability than the low molecular weight polymers.
However, polymers that complex hardness can also, if used
at high concentrations, form insoluble calcium salts which
exhibit inverse solubility [24].
Calcium ion compatibility of several polymers exposed to
thermal stress (200 °C for 20 hr) was studied using a stand-
ard test method as described previously [24]. The results
shown in Figure 10 indicate that thermal treatment of ac-
(A)
(B)
(C)
Figure 9 Optical micrograph of iron oxide dispersed in the absence of poly-
mer (A), in the presence of 1 ppm of ter-polymer (P-6) before heat treatment
(B), and in the presence of 1.0 ppm of heat treated P-6 at 200 °C for 20 hr
(C)
Tenside Surf. Det. 43 (2006) 5
rylic acid homopolymer (i. e., P-2) does not significantly im-
pact the compatibility of P-2 with calcium ion. For example,
calcium compatibility values obtained in the absence and
presence of heat treatment are 5 and 4.5 ppm polymer/
1000 mg Ca, respectively. The data presented in Figure 8
also suggest that all SA-containing co- and terpolymers are
affected by thermal treatment. With the exception of P-6,
all co- and terpolymers became significantly less tolerant to
Ca. For example, Ca ion tolerance values obtained for P-5
and P-7 are > 100 ppm before thermal stress compared to
∼ 2 ppm obtained when these polymers are subjected to ther-
mal stress (200 °C for 20 hr). Because the resultant polymer
in both cases (P-5 and P-7) is essentially a poly(acrylic acid)
P-AA, the poor compatibility obtained for both polymers is
consistent with high molecular weight water polymerized
P-AA [24].
4 Particle Size Characterization by Optical Microscopy
The iron oxide particles collected at the end of dispersancy
experiments were also evaluated for particle morphology
and size by optical microscopy. Figure 9 presents micro-
graphs of iron oxide particles in the absence of polymer (Fig-
ure 9 A), in the presence of 1.0 ppm P-6 (Figure 9 B) and in
the presence of 1.0 ppm P-6 heat treated at 200 °C for 20 hr
(Figure 9 C). It is evident from Figures 9 A and 9 B that
whereas ter-polymer exhibits marked effect in breaking
down (or de-agglomerating) large iron oxide particles, heat
treated ter-polymer shows poor performance in terms of de-
agglomeration. Amjad and Zuhl [25] recently studied the ef-
fect of polymers on iron oxide particle size distribution in
aqueous solution. It was found that in the presence of poly-
mers the iron oxide particle size distribution shifts from lar-
ger particle size (> 50 micron) to smaller (< 5 micron) parti-
cle. In addition, it was also observed that heat treated co- and
ter-polymers show less effect on particle size distribution
profiles. The results obtained in the present investigation
on iron oxide dispersancy by heat treated and non-treated
polymers are consistent with the changes observed in iron
oxide particle size distribution profiles in the presence of
polymers.
5 Summary
The heat stability of several homo-, co-, and ter-polymers un-
der simulated boiler water conditions has been investigated.
The results indicate that all polymers undergo some degra-
dation under the conditions employed in this study.
For polymers before heat stress, the co- and ter-polymers
provide significantly better iron oxide dispersion than the
homo-polymers. However, after heat stress, P-6 is clearly a
better overall iron oxide dispersant than P-7 and P-8 which
performs better than co-polymer (P-5). Iron oxide dispersion
data also suggest that heat treatment of all the homo-poly-
mers tested does not significantly degrade their perform-
ance.
Heat stress testing data indicate that homo-polymers lost
slightly less molecular weight than ter-polymers which lost
less molecular weight than co-polymers. Furthermore, poly-
mer that is susceptible to heat degradation experience mole-
cular weight and performance loss as the heat treatment is
increased from 150 °C to 200 °C.
The FT-IR and NMR analysis of the polymers exposed to
heat treatment reveal that the SA containing co-polymer (P-5)
and SA and t-BuAm containing ter-polymers (P-7, P-8) under-
went more severe degradation than ter-polymer containing
sulfonated styrene (P-6).
249
Z. Amjad: Role of heat treatment on the performance of polymers as iron oxide dispersants APPAR. INFORMATION

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Received: 09. 06. 2006
Revised: 04. 08. 2006
❙ Correspondence to
Z. Amjad
Performance Coatings
Noveon, Inc.
9911 Brecksville Road
Brecksville, OH 44141
The author of this paper
Zahid Amjad, received his M.Sc. in Chemistry from Punjab University, Lahore, Paki-
stan, and his Ph.D. in Chemistry from Glasgow University, Scotland. He is currently a
Research Fellow in the Performance Coatings Group of the Noveon, Inc. His areas
of research include interactions of polymers with different substrates in aqueous
solution, and applications of water soluble and water swellable polymers in perso-
nal care, pharmaceutical, and industrial water systems.
You will find the article and additional material by enter-
ing the document number TS100312 on our website at
www.tsdjournal.com

NIR-Kameras im erweiterten Infrarot

L.O.T.-Oriel bietet Kameratypen basierend auf drei Detektor- eine großformatige Kamera mit 640 × 512 Pixel lieferbar, in
materialien an. InGaAs hat hervorragende Detektionseigen- Europa ohne jede Lizenz.
schaften im nahen Infrarot und ist daher das bevorzugte
Material zwischen 900 nm und 1700 nm. Hier übertrifft es Ansprechpartner:
an Empfindlichkeiten alle anderen Materialien. Herr Stefan Wittmer
Beim „extended“ InGaAs handelt es sich um ein dotier- L.O.T.-Oriel GmbH & Co. KG
tes InGaAs, das bis „hinauf“ zu 2500 nm eingesetzt werden Im Tiefen See 58, D-64293 Darmstadt
kann, allerdings mit deutlich reduzierter Gesamtempfind- Tel.: +49(0)61 51-88 06-63, E-mail: wittmer@lot-oriel.de
lichkeit im Vergleich zum Standardmaterial. Internet: http://www.lot-oriel.com/de
Diese Kameras benötigen daher mindestens einen drei-
stufigen Peltierkühler, um das Rauschen bei langer Integra-
tion zu reduzieren. Aber auch in der tiefgekühlten Variante
wird der Detektor des „extended“ InGaAs gegenwärtig aus-
schließlich für Anwendungen genutzt, bei denen das Objekt
intensiv strahlt, beispielsweise bei Laserstrahl-Analysen.
Eine Alternative ist die Verwendung einer MCT-Kamera
(Quecksilberkadmiumtellurid). Diesen Detektor gibt es
in einer Variante für den Spektralbereich von 850 nm bis
2500 nm. Er bietet im Vergleich zum „extended“ InGaAs ei-
ne fast vierfach höhere Quanteneffizienz und somit eine ho-
he Empfindlichkeit.
Die Herstellung von hochwertigen MCT Focal Plane-
Arrays mit nur wenigen Defekten ist zudem Routine. Die
notwendige Kühlung auf 200 K wird mit einem thermoelek-
trischen TE4-Kühler erreicht. Dadurch bleibt das Kamera-
modell XEVA-MCT kompakt mit nur 11 × 10 × 9 cm3. Die
XEVA-MCT gibt es gegenwärtig in zwei Varianten mit 60 Hz
und 100 Hz, jeweils im Vollbild 320 × 240 Pixel.
Im Vergleich zum MCT-Detektor hat der InSb-Detektor
eine ähnlich hohe Bildqualität und Empfindlichkeit im Be-
reich zwischen 1700 nm und 2500 nm, aber er erweitert
den Bereich bis 3000 nm. Ein entscheidender Nachteil des
InSb-Detektors ist allerdings die Notwendigkeit der Küh-
lung auf 77 K, die einen leistungsstarken und lebensdauer-
begrenzenden Stirling-Kühler voraussetzt. Zudem sind die
Optiken im erweiterten MID-Bereich um ein Vielfaches teu-
rer als Optiken, die lediglich bis 2,5 lm transparent sind.
Andererseits gibt es neben der Standard 60 Hz-Version und
der 100 Hz-High Speed-Variante bei InSb-Kameras eine
350 Hz-Vollbild-Super High Speed-Kamera. Zudem ist auch

250 Tenside Surf. Det. 43 (2006) 5