Energy and Buildings 87 (2015) 220–225

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Energy and Buildings

journal homepage: www.elsevier.com/locate/enbuild

Preparation and characterization of a reflective and heat insulative

coating based on geopolymers
Zhetao Zhang, Kaituo Wang, Binghui Mo, Xinfeng Li, Xuemin Cui ∗
School of Chemistry and Chemical Engineering and Guangxi Key Lab of Petrochemical Resource Processing and Process Intensification Technology, Guangxi
University, Nanning 530004, China

a r t i c l e i n f o a b s t r a c t

Article history: A reflective heat insulation coating was prepared using a geopolymer, which was mainly made of sodium
Received 23 August 2014 silicate solutions and metakaolin, as the primary film forming material before adding sericite powder,
Received in revised form 5 November 2014 talcum powder, titanium dioxide and hollow glass microspheres as fillers. This coating is a new, envi-
Accepted 8 November 2014
ronmentally friendly inorganic coating with many capabilities, such as good water-retention, simple
Available online 18 November 2014
spraying, the compacted paint, high durability, dirt resistance, high reflectivity and remarkable heat
insulation. The results indicate a titanium dioxide content of approximately 12% yields 6% hollow glass
Keywords:
microspheres yielded a reflective heat insulation coating with a reflectivity over 90% and thermal insula-
Coating based on geopolymer
Hollow glass microsphere
tion performance (internal and external surface temperature difference) of up to 24 ◦ C. These mechanical
Titanium dioxide and insulative properties could achieve the China National Standard (GB/T25261-2010).
Reflective and heat insulation © 2014 Elsevier B.V. All rights reserved.

1. Introduction aluminosilicate material belongs to a cement system and has

many good properties, such as excellent hardness and strength,
Heat insulation coatings are new, energy-saving materials strong corrosion resistance, low thermal conductivity, easy bond-
developed in recent years [1–8]. Čekon et al. found that coatings ing and high durability. In contrast to organic exterior wall coatings,
of hollow microspheres can contribute to the thermodynamic per- geopolymer-based coatings have anti-ultraviolet and anti-aging
formance up to 5% in daytime [1]. According to Guo’s study, the capability [11–13]; thus, they are more suitable for fabricating inor-
heat reflective insulation coating could reduce the exterior wall ganic exterior wall building coatings. In addition, a heat insulative
surface temperature effectively, and the maximum temperature paint, including pigments and fillers, was added to the film forming
change is about 8–10 ◦ C [4]. Jose et al. found new type of pig- material and had an important effect on the heat insulation coating
ments Y2 BaCuO5 and lanthanum–strontium copper silicates, not performance.
only possess high chemical and thermal stability, and they have In this paper, a reflective heat insulation coating was prepared
high near-infrared reflectance (61% at 1100 nm) [7,8]. All above using a geopolymer as the primary film forming material. We dis-
heat insulation coatings painted onto the building’s exterior wall cussed the influence of the types of pigments and fillers, titanium
can effectively reduce the temperatures at the surface and within dioxide content and hollow glass microsphere had on the coating’s
the building and thus protect the building, which result from the various mechanical properties and heat insulation performance.
reflection, separation and radiation of the sunlight energy can
obviously reduce the energy absorption of a building’s exterior wall,
roof, and indoor area [9]. However, above heat insulation coatings 2. Experiments and calculation
are organic binder coating so that they are easy aged under ultravi-
olet. Therefore, to seek an inorganic heat insulation coating should 2.1. Materials and experiments
be a promising option.
Geopolymers [10] are an aluminosilicate inorganic polymer In these experiments, the coatings were mainly prepared from
material formed via earth chemistry or geological synthesis. The metakaolin and commercial sodium silicate solutions. Metakaolin
was prepared from commercial kaolin calcined at 800 ◦ C for 2 h. A
commercial sodium silicate solutions with a modulus (SiO2 /Na2 O
molar ratio) of 3.3 and solid content of 38 mass% was used for the
∗ Corresponding author. Tel.: +86 0771 3233718; fax: +86 0771 3233718. alkali-activation. The following materials were also used as pig-
E-mail address: [email protected] (X. Cui). ments and fillers added to the coating: titanium dioxide, hollow

http://dx.doi.org/10.1016/j.enbuild.2014.11.028
0378-7788/© 2014 Elsevier B.V. All rights reserved.
 Z. Zhang et al. / Energy and Buildings 87 (2015) 220–225 221

Fig. 1. Process flow chart for preparing reflective and heat insulation coatings based on geopolymers.

glass microspheres and talc powder. The dispersing agent, wetting device photo (as shown in Fig. 2), holes were made in the geo-
agent, and water-retaining agent were also used to the coating so metric center of the line from the lamp axis. A black enamel and
as to promote its performances. reflected heat insulation coating was painted onto the tinplate chip.
The coating was added to an approximately 120 × 80 × 2 (mm) The dry film thickness was 90 ␮m for a fixed room temperature
steel substrate or fiber reinforced calcium silicate board. Initially, of 28 ± 1 ◦ C. A 500 W infrared lamp was used to simulate sun-
the steel substrates were cleaned using sand paper followed by light irradiating the coating. Adjusting the distance of the infrared
washing with a diluted hydrochloric acid solution, hot water, alka- lamp to the test plate controlled the surface temperature of black
line liquor, distilled water and ethanol [12,13]. The fiber reinforced enamel board at 87.8 ± 1 ◦ C. This experiment used a distance of
calcium silicate boards were cleaned using detergent and distilled 30 cm after adjustments after testing both sides of the board with
water. a surface thermometer and recording data every 10 min until the
The inorganic paints were prepared from metakaolin and temperature stabilized. Finally, this paper determined the coating
sodium silicate solutions with the additives. After mixing and stir- reflectivity calculation using a formula based on experience (Eq.
ring at high speeds to disperse evenly, the resultant slurries were (1)) [17].
used as the coating. The coating was applied by brushing onto the t1 − t2
metal plate or fiber reinforced calcium silicate board and cured at Coating reflectivity  = (1)
t2 − t3
35 ◦ C for 7 d after labeling. The coating process is explained in the
diagram in Fig. 1. where  = reflectivity, t1 = the back temperature of black enamel
The coating adhesive strength was measured according to China board, t2 = the back temperature of coating sample, t3 = room tem-
GB/T172021979 (film adhesion determination method). perature.
The coating hardness was tested according to China GB/T
173021993 (paint film hardness testing method “(double pendu- 2.3. The calculation and test of heat insulation performance of
lum stem method)). coating
The coating flexibility was measured according to China GB/T
173121993 (film flexibility determination method). A simple self-made heat insulation performance test mech-
The resistance strength was tested according to China GB/T anism and its device photo were made according to Chinese
173221993 (film impact resistance mensuration) construction industry standards (GB/T25261-2010) as shown Fig. 3,
and the cavity dimensions were 300 × 300 × 300 (mm). A temper-
ature measurement box with made from 30 mm thick polystyrene
2.2. The calculation and test of reflectivity of the coating board with a coefficient of thermal conductivity no more than
0.03 w/m after digging a 125 × 85 (mm) hole above it. The board
Based on the U.S. army standard MIL-E-46136 standard [14–16] was covered in the reserve slot above the box, sealed with adhe-
for choosing a simple reflecting solar heat test mechanism and its sive plaster and debugged at room temperature to ensure the initial

Fig. 2. Heat reflectivity testing mechanism and device photo.

222 Z. Zhang et al. / Energy and Buildings 87 (2015) 220–225

Fig. 3. Reflective insulation testing mechanism and device photo.

temperature of each piece of the model was 28 ± 1 ◦ C. The inter- form a vacuum cavity group in the coating, which creates an effec-
nal and sample temperatures were recorded in an incubator every tive heat barrier with an adiabatic effect [21]. Therefore, this study
10 min until no obvious change occurred, and an intuitive analysis used hollow glass microspheres as the functional fillers.
of the heat insulation performance for the different coatings was
performed. 3.2. The influence of titanium dioxide on the coating reflectivity
performance
3. Results and discussions
To determine the influence different rutile titanium dioxide con-
3.1. The choice of heat insulation fillers and pigments centrations had on the coating, this paper tested powders with
contents of 0%, 4%, 8%, 12%, 16%, and 20% (mass faction). These
The ability to reflect infrared radiation from a hot reflective coat- coating’s reflectivity test results are shown in Fig. 4.
ing was shown as the scattering rate. The higher the scattering rate, Fig. 4 indicates increasing the titanium dioxide content in coat-
the stronger the reflected infrared ray [18]. The scattering rate, m, ing improves the reflectivity. This result was because the space
is defined in Eq. (2): between the titanium dioxide particles in the coating decreases
with increasing content, which makes it more difficult for the
nP
m= (2) thermal radiation to enter the coating through the surface and
nR
strengthens the coating’s reflectivity. When the titanium dioxide
where nP = the refractive index for the pigment, nR = the refractive content exceeds a certain value, the reflectance also reaches a maxi-
index for the base stock. Eq. (2) indicates that, if this paper wants mum. For example, once the titanium dioxide content exceeded 8%,
a high scattering rate, it must use pigments with a high refrac- its influence on the reflectivity began to reduce.
tive index and a base stock with a low coefficient. In other words,
when the difference between the pigment and base stock is large, 3.3. The influences of titanium dioxide content on the heat
the coating reflects more sunlight [19]. The differences in the base insulation coating performance
stock types have less effect on the heat insulation performance than
the refractive index of the pigment and packing. This experiment Heat insulation coating were prepared using rutile titanium
used a geopolymer as the base. Rutile titanium dioxide has a refrac- dioxide with 4%, 8%, 12%, 16%, 20% (mass fraction) content pre-
tive index of 2.76, which had the highest infrared scattering, so pared. Devices such as those shown in Fig. 2 were used to test
this study used it as the pigment and filler for the coating to not
only save costs but also significantly improve the heat insulation. In
addition, the radiation cooling principle indicates the atmospheric
infrared radiation mainly originates from water vapor, carbon diox-
ide, ozone and suspended particles with water vapor and carbon
dioxide. However, these material’s absorption capabilities are weak
for wavelengths within 8–13.5 ␮m, so the atmosphere has high
transmission capabilities for infrared radiation from 8 to 13.5 ␮m
[20]. This experiment used sericite and talcum powders, which
have strong thermal radiation capability within 8–13.5 ␮m, as the
fillers. They can be used as fillers to increase the film’s fullness and
prevent ultraviolet penetration from weathering the film resistance
and heat resistance; therefore, they also impact the reflective heat
insulation capabilities of the film. For all preservation and heat insu-
lation materials, the heat insulation coating significantly impedes
heat transfer to achieve insulation. Such coatings generally use heat
insulation aggregates, which has a low thermal conductivity coef-
ficient, as the main heat insulation additives. Because hollow glass
microspheres have low density and thermal conductivity, they can Fig. 4. Influence of titanium dioxide content on reflectivity.
 Z. Zhang et al. / Energy and Buildings 87 (2015) 220–225 223

Fig. 6. Back temperature change curve for the hollow glass microsphere content.

Fig. 5. Back temperature change curve for different test-plates.

3.5. The scanning electron microscope (SEM) analysis

the heat insulation and reflectivity of three types of board, a blank A scanning electron microscopy was used to analyze the
iron plate, a test panel with no added titanium dioxide and a coat- coating features of samples A (geopolymer based coating
ing with added titanium dioxide. Fig. 5 shows the back balance with titanium dioxide 0%, beads 0%), B (titanium dioxide
temperature curve for the different test-plate coating. 12%, beads 0%), C (titanium dioxide 12%, microspheres 4%)
Fig. 5 indicates the back temperature was 7 ◦ C lower for the and D (titanium dioxide 12%, beads 6%). We determined the
geopolymer coated test-plate than the blank test-plate and adding heat preservation capabilities of the coating from the internal
titanium dioxide lowered it 2–8 ◦ C further. Therefore, adding tita- structure.
nium dioxide significantly improves the heat insulation effect and Fig. 7A indicates coating A had an obvious surface hold with a
increasing the titanium dioxide content would increase this effect. large space and poor coating density. A little light and heat can be
This trend resulted from titanium dioxide changing the coating per- reflected by the coating surface. Compared to coating A, coating B,
formance as a type of pigment and filler with reflectivity for near which added titanium dioxide, had a dense structure and formed a
infrared and visible light due to its high refractive coefficient. Fig. 5 good film. Fig. 7B shows the titanium dioxide was evenly dispersed
also shows that a titanium dioxide content of 12 mass%, provided in the coating. This trait not only enhanced the heat reflective capa-
the highest reflectivity. This sample could reflect the most sun- bilities but also provided a great barrier to light, which provided a
light and thus reduce the coating surface temperature. However, certain adiabatic effect.
adding more than 12 mass% had a reduced effect for decreasing the Based on Fig. 7C and D, coating D (beads 6%) had a small
temperature. Therefore, consider costs, 12 mass% titanium dioxide hole in the surface not present in coating C (beads 4%). How-
additives were considered the most suitable. ever, increasing the hollow microsphere content would gradually
reduce the coating gaps and filled the pore with hollow micro-
spheres, which indicates the microspheres entered the geopolymer
3.4. The influences of hollow glass bead content on the coating
spaces to make the connection between the geopolymer and
heat insulation performance
surface tighter. Thus, this paper concludes using the right
amount of microspheres could improve the coating density and
Hollow glass microspheres have a large specific surface area,
smooth the film. The beads scattered uniformly in the coating
and light at the coating surface could pass through the hollow glass
and formed vacuum cavities that provided heat insulation to
microsphere and produce multiple reflections. Simultaneously,
coating.
hollow glass beads have low thermal conductivity that can enhance
the heat insulation performance. This study, used 12 mass% tita-
nium dioxide with 0%, 2%, 6%, 10% (mass faction) of selected hollow 3.6. Composite heat insulation coating properties base on
glass microspheres added to prepare coatings, and the resultant geopolymer
devices (as shown in Fig. 2) were used to test the heat insulation
effect. The results are shown in Fig. 6. A template of the heat insulation coating on a geopolymer was
Fig. 6 shows adding the microbeads lowers the temperature prepared based according to the relevant standards (GB/T25261-
2–7 ◦ C relative to the other back temperatures. Increasing the 2010) and tested for its physicochemical properties. The results are
microsphere content gradually improved the heat insulation of the shown in Table 1.
coating, and the back temperature of the test plate containing 6% The thermal insulation (temperature difference), T/◦ C, was the
was the lowest with the best heat insulation. Increasing the content back temperature difference between a blank sample and the test
further had decreasing capability to reduce the equilibrium back plate due to the reflective heat insulation geopolymer coating.
temperature. This result illustrated the insulation performance of
the coating improved to varying degrees. In addition, increasing 3.7. Advice on evaluation standard for geopolymeric heat
the hollow microsphere content increases the coating viscosity and insulation coating
they become difficult to disperse, which influences the construction
performance. The film became brittle after curing. Therefore, based Due to the China National Standard of the heat insulation coat-
on the comprehensive index, a microsphere content of 6 mass% was ing that is usually fitting for organic coating, therefore we should
the most appropriate. develop and propose a systematic methodology for evaluating the
224 Z. Zhang et al. / Energy and Buildings 87 (2015) 220–225

Fig. 7. SEM image of the (A) coating A (5k times); (B) coating B (5k times); (C) coating C (10k times); (D) coating D (10k times).

Table 1 4. Conclusions
Properties for inorganic building coatings based on the geopolymer.

Item Qualification For a geopolymer film forming material, this study selected
Condition in container Uniformity, no agglomeration rutile titanium dioxide, sericite powder, talc and hollow glass
after mixing beads as fillers by screening their functions to prepare an inor-
Application property Brush two way barrier-free ganic heat insulation coating with good performance. Titanium
Film appearance Normal dioxide played a key role in the reflectivity. Increasing the tita-
Contrast ratio (white and light color) >0.95
nium dioxide content gradually increased the coating reflectivity.
Heat storage stability (30 d) No agglomeration, mold
spoilage, but some Specifically, adding 12 mass% of titanium dioxide to the coating had
condensation a positive effect on the application, mechanical, optical and heat
Low temperature storage stability (3 times) No agglomeration, condensed insulation properties of the coating. Experiments using 12 mass%
Tack-free time/h <2
titanium dioxide determined the heat insulation effect was best
Hard drying time/h <6
Washability (time) >2000 when 6 mass% of microspheres were used. The geopolymer was
Water resistance (168 h = 7 d), >30 d No blister, crack, flake, allow a high strength material with rapid hardening, volume stability,
slightly off powder strong interface binding force, chemical corrosion resistance, high
Alkali resistance (168 h = 7 d), >14 d No blister, crack, flake, allow temperature resistance, aging resistance and good durability. An
slightly off powder
inorganic geopolymer was selected as the film material. By adding
Resistance to temperature fluctuations (10 No blister, crack, flake, allow
times) slightly off powder functional packing, we created a coating with a reflectivity above
Stain resistance/% ≤20 90%, and the thermal insulation temperature difference reached
Artificial aging resistance (white and light No blister, crack, flake, 24 ◦ C. This heat insulation effect was obvious and could be use in
color) (I 800 h) efflorescence ≤ class 1,
buildings to conserve energy.
discoloration ≤ class 2
Reflectivity/% >85
Thermal insulation (temperature 24
difference) T/◦ C Acknowledgments

This work was supported by the Chinese Natural Science Fund

(grant: 51262002) and the Guangxi Natural Science Fund (grant:
geopolymeric heat insulation coating. Based on the same measured 2012GXNSFDA053003).
method and mechanism for reflectivity and heat insulation per-
formances, the geopolymeric heat insulation coating maybe referee
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