Pigment & Resin Technology

Double layer water-borne heat insulation coatings containing hollow glass microspheres (HGMs)
Dawei Zhang Haiyang Li Hongchang Qian Luntao Wang Xiaogang Li
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Dawei Zhang Haiyang Li Hongchang Qian Luntao Wang Xiaogang Li , (2016),"Double layer water-borne heat insulation
coatings containing hollow glass microspheres (HGMs)", Pigment & Resin Technology, Vol. 45 Iss 5 pp. 346 - 353
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 Double layer water-borne heat insulation
coatings containing hollow glass
microspheres (HGMs)
Dawei Zhang, Haiyang Li, Hongchang Qian, Luntao Wang and Xiaogang Li
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing, China

Abstract
Purpose – This study aims to construct a double layer heat insulation coating based on hollow glass microspheres (HGMs) and to investigate the
effect of particle size on barrier property and heat insulation performance.
Design/methodology/approach – The waterborne double layer coating was composed of an anticorrosive epoxy ester primer and an
HGM-containing silicone acrylic topcoat. With varied HGM sizes (20 ␮m, 40 ␮m, 60 ␮m and a 1:3 w/w mixture of 20 and 60 ␮m particles), the
coating was immersed in 3.5 wt% NaCl solution for 28 days and was then subjected to a salt spray test for 450 h. The barrier properties of the
coating were evaluated through electrochemical impedance spectroscopy. Heat insulation performance was examined using a self-made device.
Findings – The addition of HGMs decreased the barrier properties of the coating by creating particle/resin interfaces for water penetration. In the
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HGMs-containing coatings, the use of larger HGMs showed relatively good barrier properties because of the lower particle density. The coating with
smaller particles yielded a higher heat insulating capacity as indicated by lower equilibrium temperatures.
Research limitations/implications – Future work will be focused on improving the barrier properties of the coating. Field exposure tests should
also be performed to assess the long-term performance of the coating.
Practical implications – The mechanical properties of the coatings in this study also implied that HGMs can be used to develop scratch-resistant
and impact-resistant coatings. Other potential applications for further studies include the uses of HGMs for coatings with improved fire retardancy
and electromagnetic interference shielding.
Originality/value – A double layer coating was developed to provide balanced performance on both anticorrosion and heat insulation. The effects
of HGM size were particularly highlighted.
Keywords Corrosion, EIS analysis, Heat insulation, Waterborne coating
Paper type Research paper

Introduction 2011; Guo et al., 2012; Song et al., 2013). They have also been
used on the surfaces of oil tanks or cargo containers to decrease
As environmental problems have increased, waterborne
their internal temperatures; as a result, safety risks associated
coatings have been extensively investigated because of their
with overheating are reduced. In general, the heat insulating
low volatile organic compound (VOC) content and the
performance of a coating can be improved by one or a
environmental friendliness thereof. In various applications,
combination of the following three strategies: first of all, heat
these coatings have been used to replace solvent-borne
insulation can be enhanced by increasing the reflectivity of a
coatings to mitigate corrosion because of their barrier effects
coating surface to reduce energy penetration (Hernandez-
on corrosive species such as water, oxygen and chloride ions
Perez et al., 2014). Radiation-type coatings are another major
(Sorensen et al., 2009). In complicated working environments
class of heat insulation coatings that rely on particulate fillers,
or under special requirements, it is also expected that the
such as ferric oxide and titanium dioxide, that can emit the
coatings can possess other desirable functionalities, such as
absorbed heat from the coating surface (Sadineni et al., 2011).
hydrophobicity (Liu et al., 2013), bacterial resistance (Yilmaz
Intrinsic insulating performance can also be improved using
et al., 2014) or heat insulating property (Wang et al., 2010).
additives with a low coefficient of thermal conductivity
Coatings with an excellent heat insulating performance are
(Temuujin et al., 2009). Hollow glass microspheres (HGMs) are
necessary to conserve energy. For example, heat insulation
rigid porous particles that can be used as excellent heat insulating
coatings have been applied to reduce temperatures on building
fillers because of the very low thermal conductivity of air inside
surfaces (Synnefa et al., 2006; Shen et al., 2011; Karlessi et al.,

The current issue and full text archive of this journal is available on
Emerald Insight at: www.emeraldinsight.com/0369-9420.htm
This work is supported by National Natural Science Foundation of China
(No. 51401018), the National Basic Research Program of China (973
Program project, No. 2014CB643300) and China Postdoctoral Science
Foundation (2014M560887).

Received 27 April 2015

Pigment & Resin Technology Revised 7 September 2015
45/5 (2016) 346 –353 19 November 2015
© Emerald Group Publishing Limited [ISSN 0369-9420] 28 November 2015
[DOI 10.1108/PRT-04-2015-0041] Accepted 12 December 2015

346
 Hollow glass microspheres Pigment & Resin Technology
Dawei Zhang et al. Volume 45 · Number 5 · 2016 · 346 –353

(0.023 W/mK). HGMs are an ideal filler of heat-insulating Table I Formulation of the anticorrosive primer
coatings because of their low cost and convenient production Ingredients Wt (%)
method. For instance, waterborne heat insulating acrylic coatings
can decrease the temperature of a coated panel from 50°C to Epoxy ester emulsion 60
40-43°C, by incorporating 5-20 wt% HGMs (Sahu et al., 2013). Zinc phosphate 5
Dombrovsky (2005), Dombrovsky et al. (2007) studied the Iron oxide 15
infrared radiative properties of HGM-containing polymer Talc 10
coatings, which reduced heat loss from building surfaces at night Drier 1
because of decreased thermal radiation. In another study, the DI water 9
long-term heat insulating performance of HGMs-containing
coatings has been investigated on the exterior walls of model
Table II Formulation of the heat insulation topcoat
houses in an outdoor environment (Guo et al., 2012). The house
with heat insulating coating exhibited not only lower Ingredients Wt (%)
temperatures but also smaller temperature fluctuation than the Silicone acrylic emulsion 60
house with non-insulating coating. With this type of coating, the HGM 7
estimated annual savings for air conditioning electricity was ⬃5.8 Rutile TiO2 15
kWh/m2/month. Mica powder 6.25
To achieve excellent heat insulation performance, a high level Kaolin 3.75
of functional fillers are often needed in the coatings. Dispersing agent 1.25
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Nevertheless, this may undesirably result in an increase in the
amount of micro-defects (Hao et al., 2011) and a decrease in the
adhesion of coating to metal substrate (Mirabedini et al., 2008);
both phenomena can damage the protectiveness of coatings
against corrosive attacks. To overcome these problems, a
multilayer coating system can be applied for a balanced
performance contributed by a heat insulation topcoat and an
anticorrosive primer. In this study, we developed a double layer
coating system composed of a waterborne epoxy ester primer and
a waterborne heat insulation topcoat containing HGMs with
different sizes. Electrochemical impedance spectroscopy (EIS)
measurements were performed during long-term immersion in
3.5 wt% NaCl solution to evaluate coating barrier performance
against corrosion. The decay of the coating resistances of the
topcoat and the primer was individually tracked to clarify the
effect of HGM size on the barrier property of the coating systems.
The heat insulating capacity of the coatings was evaluated and
compared with that of an HGM-free coating.
Experimental
Materials
The waterborne epoxy ester emulsion and the drier (DPA-01)
for the anticorrosive primer were received from the Marine
Chemical Research Institute of China. Zinc phosphate was
provided by the Guangxi Research Institute of Chemical
Industry; talc powder was supplied by Haiyan Co. Ltd. For the
heat insulation topcoat, hollow glass microspheres (3M) with
varied diameters of 20 ␮m, 40 ␮m, 60 ␮m and a mixture of 20
and 60 ␮m (1:3, w/w) were used. The waterborne silicone acrylic
emulsion (B40) was obtained from Donglian Co., Ltd. Rutile
TiO2 was purchased from Du Pont. Mica powder was obtained
from Yongfeng Co. Ltd. Kaolin was received from Tuoyin Co.
Ltd. Dispersing agent (BYK154), levelling agent (BYK345) and
defoaming agent (BYK022) were supplied by Altana. All other
reagents were obtained from Sigma.
To prepare the coatings, all ingredients except HGMs were
mixed using a high-speed dispenser. Afterward, HGMs with a
predetermined weight were added to the slurry and manually
mixed to avoid microsphere breakage. The exact formulations of
the primer and the topcoat are shown in Tables I and II,
respectively.
Levelling agent 1.25
Defoaming agent 1.25
Ethylene glycol monobutyl ether 1.25
DI water 3
Preparation of specimens and coatings
Q235 carbon steel specimens (150 mm ⫻ 75 mm ⫻ 0.5 mm)
were sequentially polished using abrasive papers of 80, 240
and 400 grit followed by cleaning with ethanol and acetone.
The anticorrosive primer was applied on the steel substrate by
brushing and subsequently dried in air for 30 min. After three
brushes, the primer was allowed to cure at room temperature
and humidity for a week. The thickness of the obtained primer
was ⬃50 ␮m. The heat insulation coating was applied on top
of the primer in a similar manner. After three brushes, the total
thickness of the double layer coating was ⬃175 ␮m.
Characterisations
Surface morphology
The coating specimens were sputter coated with Au and
observed under a scanning electron microscope (SEM, FEI
Quanta 250) to investigate the surface morphology.
Mechanical tests
● Bending test: The flexibility of the coatings was assessed via
a bending tester according to ISO 1519:2011, by which the
coated tin plates were subjected to bending round a
cylindrical mandrel. For each composition of the coatings,
mandrels with successively decreased diameters were used
and the first mandrel over which the coating began to crack
was determined.
● Scratch resistance: The scratch resistance of the coating was
measured by a pencil hardness tester according to ISO
15184:2012. In this test, the coated steel panel was
scratched by a pencil fixed at 45° horizontal to the coating
surface under a vertical load of 7.5 N. The hardest pencil
grade which did not damage to the coating was defined as
the pencil hardness of the coating.
● Impact test: The impact strength of the coating was
examined according to the Chinese national standard of

347
 Hollow glass microspheres
Dawei Zhang et al.
GB/T 1732:1993. In this test, the coatings on tin plates
were subjected to free falling dart (1 kg) at a certain height.
The maximum height from which the falling dart would
not induce any damage to the coating was recorded.
● Adhesion test: The adhesion performance was determined
by the Chinese national standard of GB/T 1720:
1979(1989), in which a series of overlapping circular
scratches were made on a coated steel panel with a stylus.
Coating delamination was examined visually and graded
from 1 (highest adhesion) to 7 (lowest adhesion). The
principle of the test method is similar to that of ISO 1518
(Zheng et al., 2013).
Electrochemical impedance spectroscopy analysis
EIS measurements were performed through long-term
immersion in 3.5 wt% NaCl solution with a PARSTAT 2273
system over the frequency ranging from 105 Hz to 10⫺2 Hz at
open circuit potential with a 20 mV potential perturbation. A
three-electrode cell was used, consisting of a saturated calomel
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electrode as a reference electrode, a platinum electrode as a
counter electrode and the coated sample as a working
electrode. The working area of the coating was ⬃3.14 cm2.
The obtained EIS spectra were fitted to equivalent circuit
models by using ZsimpWin software. All measurements were
repeated at least twice to ensure reproducibility.
Salt spray test
Salt spray test was performed for 450 h by using ATLAS
CCX-2000 in accordance with the standard method of ISO
9227:2012. The edge and backside of the specimen were
covered by water-resistant tapes and sealed with silicone resin.
Heat insulation testing
A self-made device was constructed (Figure 1); the device
consisted of an expanded polystyrene (EPS) box,
thermometers, infrared heat lamps and holders. The
dimension of the EPS box was 420 mm ⫻ 210 mm ⫻ 260
mm, and the wall thickness was 25 mm. Two rectangular
holes (140 mm ⫻ 70 mm) with a separation distance of 100
mm were created on the top surface of the box to hold the
painted specimens. A 300 W infrared heat lamp was placed
400 mm above the specimens. A thermometer was installed at
the centre of the back surface of each specimen, where the
temperature change was tracked for 30 min. The reported
temperatures were average values of two measurements for
each specimen.
Figure 1 Schematic of the device used in heat insulation tests
348
Pigment & Resin Technology
Volume 45 · Number 5 · 2016 · 346 –353
Results and discussion
Surface morphology
Figures 2(a) – (d) shows the SEM images of the top surfaces
of the double layer coatings containing differently sized
HGMs. In each coating, HGMs are uniformly distributed
without any agglomeration because of the relatively inert
surface of the glass. For a given weight (7 wt% in this case),
smaller particles correspond to a larger quantity, as well as a
larger total surface area. The particle densities are lower for
coatings with 40 and 60 ␮m HGMs than that with 20 ␮m
HGMs; the coating matrices are more continuous in the
former than in the latter. A heat insulation topcoat with a 1:3
wt ratio mixture of 20 and 60 ␮m HGMs was also prepared
[Figure 2(d)]. This is expected to produce a more efficient
packing of the particles (Zhang et al., 2012). A blank coating
without any HGM was also similarly prepared as a control
[Figure 2(e)]. The surface of the blank coating is much
smoother and contains fewer defects compared to the coating
with HGMs.
Mechanical properties
The mechanical properties of the coatings were evaluated with
four different mechanical tests and the results were
summarised in Table III. In the bending tests, the blank
specimen exhibited the highest flexibility because bending it
over a mandrel with 2 mm in diameter did not produce any
crack on the coating surface. Addition of HGMs, which are
highly rigid, has significantly decreased the flexibility of the
coatings. With increasing quantity of HGMs in the coating,
mandrels with larger diameters were needed. Because of the
rigidity of HGMs, the scratch resistance of the coating slightly
improved as indicated by the increased pencil hardness from
less than 6B (blank specimen and coating with 60 ␮m HGMs)
to 4B (coating with 20 ␮m HGMs). All compositions have
demonstrated excellent impact and adhesion performances.
Their surfaces remained undamaged even after impacts with
dropping darts from 50 cm high (apparatus limit). Added to
the topcoats, the HGMs did not adversely affect the adhesion
of the coatings to the steel substrates, which was primarily
induced by the primers.
Electrochemical impedance spectroscopy analyses
EIS measurements were performed at 2 h, 4 h, 1, 4, 8, 16 and
24 days during immersion tests in 3.5 wt% NaCl solution to
compare the barrier properties of the coatings with different
HGM sizes. Figure 3 presents the variation of Nyquist plots
after different immersion periods. For all coatings, two
capacitive arcs were observed after 2 h of immersion,
indicating that water has already penetrated through coating
defects and reached the metal substrate. The arc at high
frequencies was correlated with the combined barrier
performance of the topcoat and the primer. A very small arc
was observed at low frequencies and is attributed to the
corrosion reactions occurring at the metal substrate.
Interestingly, all coatings showed an increase in the diameter
of the capacitive arc, which reached the maximum at a certain
point. According to previous studies, this has been associated
with the increased amount of reaction products formed by
active pigments, such as zinc phosphates, which enhance the
overall barrier function of coatings. For example, Hao et al.
 Hollow glass microspheres Pigment & Resin Technology
Dawei Zhang et al. Volume 45 · Number 5 · 2016 · 346 –353

Figure 2 SEM morphologies of the double layer coatings containing differently sized HGMs: (a) 20 ␮m; (b) 40 ␮m; (c) 60 ␮m; (d) 1:3 (w/w)
mixture of 20 and 60 ␮m HGMs; and (e) a blank coating (no HGM). Scale bar is 300 ␮m
Downloaded by George Mason University At 21:41 04 October 2016 (PT)

Table III Mechanical properties of the coatings containing differently capacitive arc at high frequencies [Figures 3(b), (d), (f), (h)
sized HGMs and (j)]. After 24 days of immersion, the HGMs-containing
Bending test Pencil Impact test Adhesion coatings exhibited the characteristic Warburg diffusion tails in
Sample (mm) hardness (cm) grade the low-frequency range of Nyquist plots. This indicates that
continual diffusion pathways were already formed in this
20 ␮m 13 4B ⬎50 1
stage. After 24 days of immersion, the blank coating did not
40 ␮m 12 5B ⬎50 1
show a Warburg diffusion behaviour on the Nyquist plot
60 ␮m 10 ⬍6B ⬎50 1
[Figure 3(j)], suggesting a higher barrier property than the
Mixed 13 6B ⬎50 1
HGMs-containing coatings.
Blank ⬍2 ⬍6B ⬎50 1
The entire coating deterioration process can be divided into
three stages: early stage when the barrier effect of zinc
showed that zinc phosphate-containing epoxy coatings can phosphate is stronger than the damages caused by water
exhibit an enhanced barrier property during an immersion test penetration in the coating; mid-stage when the effect of water
in artificial seawater for 60 days when the pigment volume penetration has outweighed the actions of zinc phosphates;
concentration (PVC) of zinc phosphate reached 30 per cent and end stage when massive coating failure has occurred and
(Hao et al., 2013). This phenomenon can be explained by two Nyquist plots showed the characteristic Warburg diffusion.
possible mechanisms. First, the solvated phosphate ions can Figure 4 illustrates the equivalent electric circuits to describe
react with steel in the presence of oxygen to form phosphating these coating deterioration processes. In the early and
films composed of compact corrosion products and mid-stages, the same circuit was adopted [Figure 4(a)], where
phosphatisation products (Shao et al., 2009; Hao et al., 2013). Rs is the resistance of NaCl electrolyte. Rc1 and Qc1 are the
Second, it is also possible for the hydrolysed zinc phosphate to resistance and the constant phase element (CPE) of
induce a pore plugging effect which can block the coating the topcoat, respectively. Rc2 is the coating resistance of the
defects, enhance the bond formation at metal/coating interface primer, and the corresponding CPE was denoted as Qc2. Rct
and reduce the chance of delamination (Beiro et al., 2003; and Qdl are the charge transfer resistant and the CPE of the
Attar, 2005; Fernandez-Perez et al., 2014). To some extent, electric double layer, respectively. In the end stage [Figure
the actions by zinc phosphate can block the penetration of 4(b)], a Warburg resistance (Zw) was serially added to Rc2 to
corrosive electrolytes. However, the deteriorating effect from describe Warburg diffusion.
continuous water ingress under prolonged immersion has The coatings containing larger HGMs showed larger
eventually counteracted the additional gain of barrier property capacitive arcs in the Nyquist plots, demonstrating higher
by zinc phosphates because of the intrinsically low barrier barrier properties. It should be also noted that the largest
performance of waterborne coatings. On Nyquist plots, this capacitive arcs showed up only after 1 day of immersion
was shown as a gradual decrease in the diameter of the for coatings with 20 ␮m HGMs and mixed HGMs. However,

349
 Hollow glass microspheres Pigment & Resin Technology
Dawei Zhang et al. Volume 45 · Number 5 · 2016 · 346 –353

Figure 3 Nyquist plots of the double layer coatings containing HGMs with the size of (a-b) 20 ␮m; (c-d) 40 ␮m; (e-f) 60 ␮m; (g-h) 1:3 (w/w)
mixture of 20; and 60 ␮m HGMs; and (i-j) a blank coating
9.0 x 105 9.0 x 105
20μm-2h 20μm-1d
20μm-4h 20μm-4d
20μm-1d 20μm-8d
20μm-16d
20μm-24d

(ohm.cm 2)

(ohm.cm 2)
6.0 x 105 6.0 x 105

img

img
3.0 x 105 3.0 x 105

Z
0.0 0.0
0.0 3.0 x 105 6.0 x105 9.0 x 105 0.0 3.0 x 105 6.0 x105 9.0 x 105
Zre (ohm.cm2) Zre (ohm.cm2)

(a) (b)

1.8 x106 1.8 x106

40μm-2h 40μm-8d
40μm-4h 40μm-16d
40μm-1d 40μm-24d
40μm-4d
(ohm.cm 2)

Zimg (ohm.cm 2)
1.2 x106 40μm-8d 1.2 x106
Downloaded by George Mason University At 21:41 04 October 2016 (PT)

img

6.0 x105 6.0 x105

Z

0.0 0.0
0.0 6.0 x105 1.2 x106 1.8 x106 0.0 6.0x105 1.2x106 1.8x106
Zre(ohm.cm) 2
Zre(ohm.cm)2

(c) (d)
6
1.8 x10 1.8 x106
60μm-2h 60μm-8d
60μm-4h 60μm-16d
60μm-1d 60μm-24d
60μm-4d
60μm-8d
1.2 x106 1.2 x106
Z (ohm.cm2)

Z (ohm.cm2)
img

6.0 x105
re

6.0 x105

0.0 0.0
0.0 6.0x105 1.2x106 1.8x106 0.0 6.0x105 1.2x106 1.8x106
Zre(ohm.cm2) Zre(ohm.cm 2)

(e) (f)

1.5 x106 1.5x106

mixed-2h mixed-1d
mixed-4h mixed-4d
mixed-1d mixed-8d
mixed-16d
mixed-24d
6
1.0 x10 1.0x106
Z (ohm.cm2)

Zre(ohm.cm2)
img

5
5.0x10 5.0x105

0.0 0.0
0.0 5.0 x105 1.0 x106 1.5 x106 0.0 5.0 x105 1.0 x106 1.5 x106
Zre(ohm.cm2) Zre(ohm.cm2)

(g) (h)
7
6.9 x107 9.0x10
1.0 x 107
blank-2h blank-16d
blank-4h blank-24d
blank-1d
blank-4d
7 5.0 x 106 blank-8d 7
Zimg/ohm.cm2

4.6 x10 6.0x10

/ohm.cm2

blank-16d

0.0
img

0.0 5.0 x 106 1.0 x 107 7

7
2.3 x10 3.0x10
Z

0.0 0.0
0.0 2.3x107 4.6 x107 6.9 x107 0.0 7
3.0 x 10 6.0 x10
7
9.0 x 10
7

Zre/ohm.cm2 Zre/ohm.cm2

(i) (j)

350
 Hollow glass microspheres Pigment & Resin Technology
Dawei Zhang et al. Volume 45 · Number 5 · 2016 · 346 –353

Figure 4 Equivalent electric circuits in (a) early stage, (b) mid-stage
and (c) end stage
this was observed after 8 days for coatings with 40 and 60 ␮m
HGMs. In the coatings, water preferably diffuses through the
interfaces between HGMs and the coating matrix (van der
Wel and Adan, 1999). When smaller HGMs or mixed HGMs
were used, more diffusion pathways were likely created in the
topcoat because a larger interfacial area was formed between
the particles and the coating matrix. This would lead to a more
rapid decrease in the barrier property of topcoat and facilitate
water penetration to the primer. This also explains why it took
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separately tracked to have a better view of the effects of HGM
size on the barrier properties of each coating. The resistances
of the topcoat and the primer were compared, and the results
showed that the majority of barrier function was provided by
the anticorrosive primer. For the HGMs-containing coatings,
larger particles generally produced higher coating resistance of
the topcoat; however, the coating resistance gradually
decreased as immersion proceeded [Figure 5(a)]. Similarly,
higher coating resistances of the primers were observed when
40 and 60 ␮m HGMs were used. In all cases, the coating
resistances of the primers initially increased and then
decreased during the immersion; this finding was well
correlated with the results shown in the Nyquist plots. The
highest coating resistances of the primers were detected after 1
day of immersion for the coatings containing 20 ␮m and
mixed HGMs, after 8 days for the coatings containing 40 and
60 ␮m HGMs and after 16 days for the blank coating.

longer time for coatings with larger HGMs to show the
maximum diameter in the capacitive arc. In the absence of
HGMs, the water penetration in the blank coating was
significantly reduced. The Nyquist plot showed a much larger
diameter of the capacitive arc, which continued to grow until
16 days of immersion. In Figures 5(a) and (b), the variations
of the coating resistances of the topcoat and the primer were
Salt spray test
The coated specimens were also subjected to salt spray tests
for 450 h to further evaluate the barrier performance of the
coatings with differently sized HGMs. Figure 6 illustrates the
surface morphologies at the end of the tests, the trend of which
correlates well with the results of the EIS measurements. The
coating with 60 ␮m HGMs and the blank coating which had

Figure 5 Variation of coating resistance during immersion in 3.5 wt% NaCl solution: (a) topcoat; and (b) primer
6 7
4 x 10 4x10
20 μm 20μm
7
3x10
6 40 μm 3x10 40 μm
60 μm 60 μm
7
6 mixed 2x10 mixed
2x10
blank blank
Rc2(ohm.cm2)

7
1x10
Rc1(ohm.cm2)

6
1x10
4
3x10 4x10
5

4 5
2x10 3x10
5
1x10
4 2x10
5
1x10
0
0
2h 4h 1d 4d 8d 16d 24d 2h 4h 1d 4d 8d 16d 24d
Time Time
(a) (b)

Figure 6 Morphologies of the double layer coatings containing (a) 20 ␮m; (b) 40 ␮m; (c) 60 ␮m; (d) 1:3 (w/w) mixture of 20 and 60 ␮m
HGMs; and (e) a blank coating after 450 h of salt spray tests

(a) (b) (c) (d) (e)

351
 Hollow glass microspheres
Dawei Zhang et al.
fewer water diffusion pathways exhibited excellent corrosion
protection with little change in appearance. Rust formation
was more intense on the coating surface when the HGM size
was reduced, indicating a decreased protection over the steel
substrate. The most severe corrosion was observed on coating
with mixed particle size, as shown by the large rust coverage
and blistering. Similar to the EIS results, this finding was
possibly attributed to the high packing efficiency between
large and small particles, which formed more interconnected
pathways for water penetration.
Heat insulation
Heat insulation tests were performed starting at ambient
temperature until equilibrium temperatures (Teq) were
achieved. In this study, the equilibrium temperature was
defined as the temperature with minimal fluctuations (less
than 1°C) within 5 min. Figure 7 shows the variations of
temperatures measured at the back surface of the steel
specimens with heat insulation coatings and a HGM-free
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coating as a control. Under the infrared lamp, the back surface
of the control specimen underwent a rapid temperature
increase and reached an equilibrium temperature of 72.4°C
after 30 min. The coating with 60 ␮m HGMs did not
demonstrate much improvement in the heat insulating
property, with only a minor decrease in the equilibrium
temperature. By comparison, the addition of smaller HGMs
clearly induced a more effective heat insulation as indicated by
the slower increases in temperature and significantly lower
equilibrium temperatures. This finding is attributed to the
increasing particle density of heat insulating HGMs in the
coating systems. The optimum heat insulation was observed in
the coating with 20 ␮m HGMs whose equilibrium
temperature was ⬃10°C lower than that of the blank coating.
The coating with 40 ␮m HGMs exhibited the most balanced
overall performance including not only an excellent heat
insulation (⌬Teq ⬃8°C), but also good anticorrosive
performances as revealed by EIS and salt spray tests.
Conclusions
In summary, a double layer waterborne coating system was
developed based on an epoxy ester primer and a heat
Figure 7 Heat insulating performance of the double layer coatings
with differently sized HGMs
70
60
Temperature (oC)
50
40
30
20
0 5 10 15 20 25
Time (min)
Pigment & Resin Technology
Volume 45 · Number 5 · 2016 · 346 –353
insulation topcoat containing differently sized HGMs. The
barrier properties and heat insulating performance of the
coatings were investigated; the following conclusions can be
drawn:
● In the initial period of immersion, EIS analysis revealed
that the barrier properties of the coatings were enhanced;
this finding may be attributed to the hydrolysis of the zinc
phosphate anticorrosive pigment. After reaching the
maximum, the barrier property of the coatings decreased
as water penetration continued.
● EIS measurements and salt spray tests demonstrated that
the addition of HGMs created pathways for water
penetration at the particle/resin interfaces and thereby
significantly lowered the barrier properties of the coating
against corrosion. In the HGMs-containing coatings, the
use of larger HGMs led to higher barrier properties
because of the lower particle density.
● The coatings containing smaller HGMs showed better
heat insulating performance because of the higher particle
density in the coating matrix. Among the differently sized
HGMs, 20 ␮m HGMs exhibited the optimum heat
insulation, and the equilibrium temperature was
approximately 10°C lower than that of the blank coating.
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Corresponding author
Dawei Zhang can be contacted at: dzhang@ustb.edu.cn