coatings

Article
IPN Polysiloxane-Epoxy Resin for High Temperature
Coatings: Structure Effects on Layer Performance
after 450 ◦ C Treatment
Simone Giaveri 1,† , Paolo Gronchi 1, * ID
and Alessandro Barzoni 2
1 Department of Chemistry, Material and Chemical Engineering, G. “Natta”, Politecnico di Milano,
P.za Leonardo da Vinci 32, 20133 Milano, Italy; [email protected]
2 Akzo Nobel Coatings, Via Silvio Pellico, 10, 22100 Como, Italy; [email protected]
* Correspondence: [email protected]; Tel.: +39-02-2399-3274
† Present address: Institute of Materials, École Polytechnique Fédérale de Lausanne, EPFL, Route Cantonale,
1015 Lausanne, Switzerland.

Academic Editors: Assunta Marrocchi and Maria Laura Santarelli

Received: 23 October 2017; Accepted: 22 November 2017; Published: 28 November 2017

Abstract: Coatings for high temperatures (HT > 400 ◦ C) are obtained from interpenetrating polymer
network (IPN) binders formed by simultaneous polymerization of silicone and epoxide pre-polymers.
A ceramic layer; mainly composed of silica and fillers; remains on the metal surface after a thermal
treatment at 450 ◦ C. The layer adhesion and the inorganic filler’s distribution have been investigated
by, firstly, exchanging the organic substituents (methyl and phenyl) of the silicone chains and,
secondly, by adding conductive graphene nanoplatelets with the aim to assure a uniform distribution
of heat during the thermal treatment. The results are evidence that different substituent ratios affect
the polymer initial layout. The adhesion tests of paint formulations are analysed and were related
to instrumental analyses performed using glow discharge optical emission spectroscopy (GDOES);
thermal analyses (TG/DTA and DSC); electron microscopy with energy dispersive X-ray analysis
(SEM-EDX). A greater resistance to powdering using phenyl groups instead of methyl ones; and an
improved distribution of fillers due to graphene nanoplatelet addition; is evidenced.

Keywords: high-temperature coatings; corrosion protection; powder coatings

1. Introduction
The protection against corrosion of a metal surface with an organic or inorganic coating is the main
application for coatings [1] (the global anticorrosion coating market was estimated to be $24.84 billion
in 2017 and is projected to reach $31.73 billion by 2022, at a CAGR (Compound Annual Growth
Rate) of 5.0% from 2017 to 2022 [2]). An important demand in this sector is the protection against
thermo-oxidative corrosion of the metal parts of the internal combustion engines, turbines, and heaters
(other applications are: oven parts, chimney pipes, fireplace inserts, steam lines, furnaces, lighting
fixtures, heat exchangers, boilers, engines, exhaust stacks, and mufflers). The wall temperature reaches
400–600 ◦ C, at which point the organic binders degrade due to the chemical and thermal instability
of the C–C bonds. Traditional organic coatings for metals, like those based on acrylic and/or epoxy
polymers, are stable only up to 60–80 ◦ C; above 150 ◦ C, degradation takes place. On the contrary, the
binders based on hybrid organic–inorganic-containing polysiloxane show superior thermal stability [3].
The thermal stability increases more if an interpenetrating polymer network (IPN), with the
chains entangled one into the other in a dense network, is used as the binder [3]. Indeed, organic-
and inorganic-based monomers, or pre-polymers, mixed together, can separately self-polymerize with
different chemistries changing the material performances, an example is the thermal behaviour, from

Coatings 2017, 7, 213; doi:10.3390/coatings7120213 www.mdpi.com/journal/coatings

Coatings 2017, 7, 213 2 of 16

that obtained with the single resin one [4]. These binders, when they also contain ceramic or metallic
fillers, find application for heat resistant coatings at high temperatures [4,5]. However, the binders
previously described in the literature are intercrosslinked networks obtained with sequential reaction
steps, not with a simultaneous polymerization, using networking agents and curing. In the first
case, the compatibility between organic and hybrid polymeric materials is obtained by the formation
of covalent bonds, but thermal stability appears lower than in the simultaneous IPN obtained by
a single step.
The characterisation of silicone or IPN coatings, used as binders, relies on colour and gloss
changes, blistering, cracking, and loss of adhesion after exposures at high temperature. Loss of
gloss is produced by continuous break-down of the organic chains at the surface. However, when
the phenomenon becomes so strong and extensive, until the complete degradation of the binder,
the pigment splits from the binder and chalking occurs; chalking is the term used to define the release
of pigments and particles [6,7].
The present work concerns the coatings obtained by a simultaneous polymerization of silicone
and epoxy-acrylic pre-polymers to give IPNs [4], in which the formation of physical constraints,
like polymeric domains or polymer-matrix nanocomposite distribution, affects the chalking extent.
The constraints are supposed to affect the removal of thermally-degraded organic fractions from the
coating surface. Silicone-epoxy-acrylic IPNs were selected according to their properties. Epoxy resins
are characterized by low shrinkage, easy curing and processing, and the films obtained from them
acquire excellent solvent and chemical resistance, great toughness, and good adhesive strength;
otherwise, they suffer thermal stability and pigment holding ability [7]. Silicone resins and the derived
films show superior thermal and thermo-oxidative resistance, partial ionic nature, excellent moisture
resistance, low surface energy and good flame retardant properties. Moreover, silicone resins are used
as epoxy resin modifiers [8]. Acrylics, properly reacting with epoxies, were added to improve the
mechanical properties of the coatings. With the aim of increasing IPNs thermal resistance, we examined
the properties of polymer-graphene nanocomposites to understand the behaviour of these materials at
high temperatures. Indeed, following the indications of the literature [9–11], the high graphene thermal
conductivity associated with its leaflet morphology, could promote a homogeneous thermo-oxidative
degradation of the coatings [12]. Moreover, graphene’s low permeability to all gases and salts, due to
the quasi 2D structure, appears to be an excellent candidate in anticorrosion coatings [13].
Sample films were obtained by powder paints due to the high performances and environmental
constraints, accompanied by a satisfactory and easy application [14–16]. Adhesion tests are performed
and the results, examined also to infer the powdering degree, are interpreted by the data obtained
with instrumental analyses: firstly, thermal analysis, and then GDOES and SEM.

2. Materials and Methods

2.1. Materials
The coating components were:

• As binder: (IPN polymer resin) the silicone resins (Wacker Silres®, Milano (MI), Italy) and Dow Corning
Xiameter® (Midland, MI, USA) and epoxy resins (DOW D.E.R.®, Midland, MI, USA), were added with
acrylic resins (BASF, Joncryl®, Ludwigshafen am Rhein, Rhineland-Palatinate, Germany);
• As fillers/pigments: baryte (Aprochimide Baryte, Muggiò (MI), Italy), wollastonite (Nyco Nyad,
Hermosillo, Sonora, Mexico), micro mica (Norwegian Talc, N-5355 Knarrevik, Norway), manganese
ferrite black spinel (Ferro, Cleveland, OH, USA), and graphene nanoplatelets (Directa Plus,
Lomazzo, Italy);
• As additives: benzoin (Miwon Speciality Chemical, Gyeonggi-do, Korea), flow control additive
(Estron Chemical, Calvert City, KY, USA) and fluidization additive (Evonik Industries, Essen, Germany).
Coatings 2017, 7, 213 3 of 16

2.2. Paint Formulations

Many different paint formulations were prepared (see [17] for a complete description of
formulations and a listing of prepared samples). In this paper, we considered four of them using the
compositions reported in Table 1.
The weight of each batch was 1 kg and the total ligand amount was 510 g.

Table 1. Raw materials (wt %) and sample composition of selected samples *.

Coating Composition
Raw Materials ID
S4 S6 SF1 SF2
Phenyl Silicone 25 – – –
Methyl-Phenyl Silicone – 25 25 25
BPA Epoxy Resin 11 11 11 11
Carboxyl Acrylic Resin 15 15 15 15
Pigment Black 1.5 1.5 1 1.2
Fillers (1) 46.3 46.3 46.3 46.3
Additives (2) 1.2 1.2 1.2 1.2
Graphene nanoplatelets – – 0.5 0.3
*: Batch of 1 kg each: (1) micro mica, baryte, wollastonite; (2) degassing agent, flow control additive and fluidization additive.

The components of pigment and filler inorganic mixtures are presented in Table 2, together with
the physical properties.

Table 2. Pigment and filler.

Pigments and Fillers Chemical Analysis Density (g·cm−3 ) Oil Adsorption (g/100 g) Particle Size (µm)
Pigment Black MnFe2 O4 4.5 (1) 48 (2) 0.5 (3)
Baryte BaSO4 (97%)–SiO2 (2%) 4.35 (4) 11 (5) 4 (6)
Micro Mica KAl2 (AlSi3 O10 )(OH)2 0.5 (7) 49 (8) 6 (9)
Wollastonite CaSiO3 1.04 (10) 24 (11) 9 (3)
(1) :
DIN-ISO 787 part/Teil 10; (2) : DIN-ISO 787 part/Teil 5; (3) : Median particle size; Cilas granulometer HR 850-B;
(4) :
ASTM D153-82; (5) : ASTM D281; (6) : Average particle size; (7) : Tamped density; ISO 787-11; (8) : ISO 787-5; (9) :
Median particle size; (10) : ASTM C 87; (11) : ASTM C 87.

2.3. Paint Preparation

A detailed description of the powder coatings production process is outlined in the
following list: Raw material weighting—Low temperature mixing—Extrusion—Calendering—Cooling
down—Pelletizing—Milling—Sieving—Post-additivation—Sieving, again.
An OMC Saronno EBVP30/20 co-rotating intermeshing twin screw extruder (OMC, Saronno (MI)
Italy) was used; right-handed and left-handed elements and kneading disks provided distributive
and dispersive mixing, extremely important in the case of nanofillers [10]. During extrusion, the
temperatures of the five screw regions were set at 15 ◦ C, 30 ◦ C, 90 ◦ C, 110 ◦ C, and 80 ◦ C respectively;
the feeding screw was set to 1.5 rpm, and torque was checked.
After calendering, −25 ◦ C cooling was performed in order to simplify the pelletizing process.
Polymeric pellets were milled by an ALPINE rod mill (HOSOKAWA ALPINE Aktiengesellschaft,
Augsburg, Germany) and later sieved using an Endecotts laboratory test (London, UK), 125-µm sieve.

2.4. Application
Powder coatings were applied on standard low-carbon, cold-rolled steel (6 cm × 20 cm) panels
after sandblasting with inert soda-lime and tempered glass microspheres, whose mean particle size was
214.6 µm. The treatment was performed manually adopting a gun-iron panel distance at about 30 cm.
Coatings 2017, 7, 213 4 of 16

Powder coatings application was performed manually using a corona charging system on a GEMA
powder gun (GEMA, Trezzano sul Naviglio, Italy), according to [18]. Powder was carefully fed into
a venturi pump and then pneumatically transported to the corona gun by a feeding gas at 1.3 bar
pressure. One hundred kilovolts were applied at room temperature at a 250-mm gun tip-substrate
distance. A flat nozzle was used, forming an elliptical powder cloud in front of the gun. Then,
a 40–60 µm coating thicknesses were applied in order to maximize the thermal resistance. Curing was
performed in a Thermo Scientific Heraeus batch oven (Thermo Fisher Scientific, Waltham, MA, USA)
at 210 ◦ C for 20 min. High-temperature tests (HT) were performed at 450 ◦ C for 12 h.

2.5. Instrumental Methods

The thickness of the coated panels was measured by electromagnetic induction based on Byko
test 8500 (Byko, Norvik hf, Reykjavik, Iceland). High-temperature samples with exposure at 450 ◦ C
for 12 h was performed. Paint formulations, coated on sandblasted panels, were placed in a Galli
G-21HT muffle furnace (Galli, Fizzonasco di Pieve Emanele, Italy). After exposure, specimens were
removed from the furnace to be air-cooled to room temperature for at least one hour. Inspection was
carried out according to the ASTM D2485-91 (2013) standard. Evidence of peeling, cracking, blistering,
abnormal discoloration, chalking, and loss of adhesion were checked. An adhesion cross-cut test was
performed before and after heat treatment at 450 ◦ C for 12 h according to ISO 2409:2007 (E). A six-blade
cutting Byko-cut Universal Paint Inspection Gauge (Byko, Norvik hf, Reykjavik, Iceland) with 1 mm
spaced cutting edges was used. Thermogravimetric and differential thermal analyses (TG–DTA) were
performed with a SII Seiko Instruments Exstar 6000 TG–DTA 6300 unit (Seiko Instruments, Torrance,
CA, USA). Thermal runs were set from 25 ◦ C to 800 ◦ C; an air atmosphere was used to study coatings’
thermal degradation as in real working conditions. A heating rate of 10 ◦ C·min−1 was selected.
The results were reported showing wt % vs. temperature in thermogravimetric plots, as wt %·min−1
vs. temperature in DTG graphs, and as thermocouple µV vs. temperature in DTA curves.
Differential scanning calorimetry (DSC) analyses were performed with a heat flux SII Seiko
Instruments Exstar 6000 (Seiko Instruments, Torrance, CA, USA). The selected thermal cycle was
composed of a ramp from 25 ◦ C to 300 ◦ C at a 10 ◦ C·min−1 heating rate, followed by cooling to
25 ◦ C at the same speed. The heating was then repeated with a thermal run from 25 ◦ C to 500 ◦ C at
10 ◦ C·min−1 ; a nitrogen atmosphere was used. Results were reported as mW/◦ C. Finally, the areas
under the peaks were calculated using machine software (Seiko Instruments Inc. “SII”, Iwate, Japan).
Qualitative glow discharges optical emission spectroscopy (GDOES) was performed with
a Spectruma GDA 750 analyser (Spectruma, Hof, Germany). Scanning electron microscopy-energy
dispersive X-ray spectroscopy (SEM-EDS) analyses was performed using a Zeiss EVO 50 EP-Oxford
Inca energy 200 LZ4 spectrometer (Carl Zeiss, Oberkochen, Germany).

3. Results and Discussion

Four IPN specimens were taken as representative among the many (the investigations were
performed using more than 100 preparations [17] so as to cover many parameter effects); they were
named as S4, S6, SF1, and SF2, respectively (Table 1). S4 and S6 are composed of a mixture of
three resins (silicone, epoxy, and carboxylic acrylic) together to pigment black, functional fillers, and
additives. A phenyl silicone resin is present in S4, while a methyl-phenyl silicone resin is present
S6, with the same weight fraction. In SF1 and SF2 IPNs, the same S6 formulation was maintained,
except for partial substitution of the pigment concentration by graphene nano-platelets, with different
weight fractions. Functional fillers and additives were added to decrease the amount of pyrolytic
decomposition of the organic binder and to avoid defect formation during the film-forming process,
respectively [19].
 Coatings 2017, 7, 213 
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Coatings 2017, 7, 213  5 of 15 
decomposition of the organic binder and to avoid defect formation during the film‐forming process, 
respectively [19]. 
3.1. Adhesion
decomposition of the organic binder and to avoid defect formation during the film‐forming process, 
respectively [19]. 
In order to satisfactorily prevent substrate oxidation in thermal oxidative conditions, coatings
3.1. Adhesion 
must3.1. Adhesion 
adhere to the surface on which they are applied [4,5]. Cross-cut tests were carried out to assess
In order to satisfactorily prevent substrate oxidation in thermal oxidative conditions, coatings 
film adhesion before and after heat treatment.
must adhere to the surface on which they are applied [4,5]. Cross‐cut tests were carried out to assess 
In order to satisfactorily prevent substrate oxidation in thermal oxidative conditions, coatings 
The images of the coated surfaces printed on the tapes, removed from the cross-cut areas, are
film adhesion before and after heat treatment. 
must adhere to the surface on which they are applied [4,5]. Cross‐cut tests were carried out to assess 
presentedThe images of the coated surfaces printed on the tapes, removed from the cross‐cut areas, are 
in Figures 1 and 2 in order to provide evidence of the flaking (powdering) degree. Optical
film adhesion before and after heat treatment. 
presented in Figures 1 and 2 in order to provide evidence of the flaking (powdering) degree. Optical 
microscopy has been used to obtain the high-definition images for a reliable evaluation. S6 and SF1
The images of the coated surfaces printed on the tapes, removed from the cross‐cut areas, are 
microscopy has been used to obtain the high‐definition images for a reliable evaluation. S6 and SF1 
paintpresented in Figures 1 and 2 in order to provide evidence of the flaking (powdering) degree. Optical 
formulations show the best adhesion before heat treatment and their rating is consequently
paint as
classified formulations  show  the  best 
0 (Table 3 according adhesion 
to ISO before 
2409:2007 heat a treatment 
(E)); different and  their  rating 
intensity is  consequently 
of failures was found for
microscopy has been used to obtain the high‐definition images for a reliable evaluation. S6 and SF1 
classified as 0 (Table 3 according to ISO 2409:2007 (E)); a different intensity of failures was found for 
the S4 andformulations 
paint  SF2 samples.show  the  best  adhesion  before  heat  treatment  and  their  rating  is  consequently 
the S4 and SF2 samples. 
classified as 0 (Table 3 according to ISO 2409:2007 (E)); a different intensity of failures was found for 
the S4 and SF2 samples. 

 
Figure 1. Prints of cross‐cut area on tape before thermal treatment (the clearness is worsened by the 
 
Figure 1. Prints of cross-cut area on tape before thermal treatment (the clearness is worsened by the
glue layer). 
Figure 1. Prints of cross‐cut area on tape before thermal treatment (the clearness is worsened by the 
glue layer).
glue layer). 

 
Figure 2. Prints of the cross‐cut area on tape after the thermal treatment (the clearness is worsened by 
 
the glue layer). 
Figure 2. Prints of the cross‐cut area on tape after the thermal treatment (the clearness is worsened by 
Figure 2. Prints of the cross-cut area on tape after the thermal treatment (the clearness is worsened by
the glue layer). 
the glue layer).
Coatings 2017, 7, 213 6 of 16

Table 3. Sample classification on adhesion tests (according to ISO 2409:2007 E), before and after heat
treatment (HT, 450 ◦ C 12 h; air).

Classification
Sample Assessment
Before HT After HT
Before HT: small flake separation (<5% of the analysed area);
S4 1 2 After HT: The coating has flaked along the edges and/or at the
intersections of the cuts. Failure (5–15% of the analysed area)
Before/after HT: the edges of the cuts are completely smooth;
S6 0 0
none of the squares of the lattice is detached
Before HT: the edges of the cuts are completely smooth; none of
SF1 0 1 the squares of the lattice is detached; After HT: small flake
separation (<5% of the analysed area)
Before HT: The coating has flaked along the edges and/or at the
SF2 2 1 intersections of the cuts. Failure (5–15% of the analysed area).
After HT: small flake separation (<5% of the analysed area).

After thermal treatment (the tape images, after heat treatment, are reported in Figure 2), a strong
pyrolytic decomposition of the IPN organic part was expected. Indeed, although silicone resin
backbone has high thermal stability, its organic substituents suffer strong degradation in air at
T > 300 ◦ C [20–24]. According to [20], the oxygen catalyses the silicone weight loss, the residual
part of it (the backbone) undergoes the formation of a thermally-stable and tightly-reticulated, more
inorganic than organic, network. Furthermore, the adhesion on the substrate may be promoted by the
high temperature due to element inter-phase diffusion. Thus, cross-cut tests were carried out one more
time to check the substrate coating adhesion and the silicone effect. The adhesion classification, before
and after HT, is reported in Table 3.
The S4 samples have the weakest adhesion with a worsening after HT, while the S6 and SF1
coatings remain almost stable and the SF2 samples seems to show a small increase of the adhesion
after heat treatment. Adhesion tests suggest that the phenyl amount on silicone chains have to be
reduced: phenyl silicone S4 sample indeed shows a bad result on cross-cut test after heat treatment.
In an attempt to explain the behaviour, we could hypothesize that carbon and carbonaceous residues
would remain for a longer time in the silicon oxide network and interfere with the formation of bonds
to the metal during pyrolysis due to slow combustion kinetic of aromatic substituent at 450 ◦ C.
Indications of chalking can be inferred from the images of the adhesion tests; firstly, referring
to the high degradation degree of the S4 sample (Figure 2), the tape surface does not present any
transparency over the whole cutting area caused by the de-structured binder. In this case, the phenyl
silicone resin shows a strong and intense chalking, so the cross-cut area is much darker in S4 tape in
comparison with the same area of methyl-phenyl silicone-containing samples.
For the sake of completeness, in Figure 3 we report the images of S6 and SF1 panels after heat
treatment. At the same adhesion, no shadows are present on the SF1 surface, both in and out of the
cutting area, indicating a more limited chalking.
The presence of graphene probably increases adhesion after thermal treatment as the SF2 sample
assessment is two steps before HT (Table 3, change from two to one). As expected, the chalking
increases after heating as supported by the bad transparency of the tapes, as reported in Figure 2.
However, from the visual exam of the panel instead of the tapes after HT (Figure 3), SF1 presents fewer
shadows than S6 indicating a less chalking degree. Investigating the filler amount effect, SF1 and SF2
present little and no discernible cleanliness difference on tapes.
The superior resistance to chalking produced by graphene addition may be related to enhanced
properties of polymer-graphene nanocomposites [10]. The network of graphene nanoplatelets inside the
binder matrix is supposed to increase mechanical and thermal performances at high temperatures [9,11].
Finally, thermal conductivity of the graphene sheet may favor the homogeneous degradation of the organic
part of the IPNs binder, avoiding high-temperature peaks [4].
  
Figure 3. Comparison between S6 vs. SF1 coated panels after thermal treatment. 
Coatings 2017, 7, 213 7 of 16
3.2. Thermal Analysis 
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The thermo‐gravimetric analysis (TG) provides information on thermal stability (weight loss at 
increasing  temperature)  of  coatings  after  heat  curing  (210  °C)  and  suggests  hypotheses  about  the 
degradation mechanism. All curves are characterized by two weight losses (Figure 4) according to 
the cited literature with different rates of degradation. 
The first and the second weight loss (wt %) are reported in Table 4 relative to the four examined 
samples: the total losses are in the 26%–37.3% range at high temperatures (680 °C, max). The result is 
related not only to the presence of a high amount of functional fillers in each formulation, as reported 
in Table 1, but also to the presence of silicone polymers that have high residual masses after thermal 
degradation (up to 55% for methyl‐phenyl [24]). Nevertheless, the oxidative cross‐linking reaction 
rearranges all the residual organosilanes to silica. The reaction mechanism is probably triggered by 
the  formation  of  radicals  on  side  groups  that  react  with  oxygen  and  produce  peroxide  functions 
 
which accelerate the rearrangement. Finally, in an oxidative environment, some silica may be obtained 
from the competition between volatilization of oligomers and oxidative cross‐linking [20–22,25]. 
Figure 3. Comparison between S6 vs. SF1 coated panels after thermal treatment. 
Figure 3. Comparison between S6 vs. SF1 coated panels after thermal treatment.
3.2. Thermal Analysis  Table 4. Coating weight losses (%). 
3.2. Thermal Analysis
Weight Loss (wt %)
The thermo‐gravimetric analysis (TG) provides information on thermal stability (weight loss at 
Steps  T (°C) 
increasing  temperature)  of  coatings  after  heat  curing information
The thermo-gravimetric analysis (TG) provides
S4 S6°C) SF1
(210  onsuggests 
and  thermalhypotheses 
SF2 stability (weight
about loss
the 
at increasing temperature) First step 
of coatings after heat curing ◦
280–530  15.7  (210
21.6  C) and suggests
22.7  20.6  hypotheses about the
degradation mechanism. All curves are characterized by two weight losses (Figure 4) according to 
degradation mechanism. All curves are characterized
Second step  530–680  11.1 
the cited literature with different rates of degradation. by two
14.8 weight
14.6  losses
12.4  (Figure 4) according to the
citedThe first and the second weight loss (wt %) are reported in Table 4 relative to the four examined 
literature with different ratesTotal 
of degradation. 26.8  36.4  37.3  33.0 
samples: the total losses are in the 26%–37.3% range at high temperatures (680 °C, max). The result is 
related not only to the presence of a high amount of functional fillers in each formulation, as reported 
in Table 1, but also to the presence of silicone polymers that have high residual masses after thermal 
degradation (up to 55% for methyl‐phenyl [24]). Nevertheless, the oxidative cross‐linking reaction 
rearranges all the residual organosilanes to silica. The reaction mechanism is probably triggered by 
the  formation  of  radicals  on  side  groups  that  react  with  oxygen  and  produce  peroxide  functions 
which accelerate the rearrangement. Finally, in an oxidative environment, some silica may be obtained 
from the competition between volatilization of oligomers and oxidative cross‐linking [20–22,25]. 

Table 4. Coating weight losses (%). 

Weight Loss (wt %)
Steps  T (°C) 
S4 S6 SF1 SF2
First step  280–530  15.7  21.6  22.7  20.6 
Second step  530–680  11.1  14.8  14.6  12.4   
Figure 4. Comparison of the curves describing the normalized weight losses of the S4 and S6 samples. 
Total  26.8  36.4 weight
37.3 losses
33.0 
Figure 4. Comparison of the curves describing the normalized of the S4 and S6 samples.

The first and the second weight loss (wt %) are reported in Table 4 relative to the four examined
samples: the total losses are in the 26–37.3% range at high temperatures (680 ◦ C, max). The result is
related not only to the presence of a high amount of functional fillers in each formulation, as reported
in Table 1, but also to the presence of silicone polymers that have high residual masses after thermal
degradation (up to 55% for methyl-phenyl [24]). Nevertheless, the oxidative cross-linking reaction
rearranges all the residual organosilanes to silica. The reaction mechanism is probably triggered by the
formation of radicals on side groups that react with oxygen and produce peroxide functions which
accelerate the rearrangement. Finally, in an oxidative environment, some silica may be obtained from
the competition between volatilization of oligomers and oxidative cross-linking [20–22,25].

 
Figure 4. Comparison of the curves describing the normalized weight losses of the S4 and S6 samples. 
Coatings 2017, 7, 213 8 of 16

Table 4. Coating weight losses (%).

Weight Loss (wt %)

Steps T (◦ C)
S4 S6 SF1 SF2
First step 280–530 15.7 21.6 22.7 20.6
Second step 530–680 11.1 14.8 14.6 12.4
Total 26.8 36.4 37.3 33.0
Coatings 2017, 7, 213  8 of 15 

The S4 sample shows the lowest total wt %, mainly concentrated at low temperatures. S6 and
The S4 sample shows the lowest total wt %, mainly concentrated at low temperatures. S6 and 
SF1
SF1 are
are characterized
characterized by higher
by  weight
higher  losses
weight  than
losses  S4, S4, 
than  while SF2 SF2 
while  presents an intermediate
presents  total wt
an  intermediate  %.  
total 
The similarity of the second step wt % between S6 and SF1 allowed us to conclude that weight loss
wt %. The similarity of the second step wt % between S6 and SF1 allowed us to conclude that weight 
does not depend on graphene. We have to note that, from the thermogravimetric point of view, the SF2
loss does not depend on graphene. We have to note that, from the thermogravimetric point of view, 
losses are less than both S6 and SF1, and are probably due to a different formulation (more pigment is
the SF2 losses are less than both S6 and SF1, and are probably due to a different formulation (more 
present, as reported in Table 1).
pigment is present, as reported in Table 1). 
The presence of two strong weight losses were highlighted by time differentiating the TG curves
The presence of two strong weight losses were highlighted by time differentiating the TG curves 
of S4 and S6 samples, as reported in Figure 5.
of S4 and S6 samples, as reported in Figure 5. 

 
Figure 5. Comparison of the curves describing the degradation rates of the S4 and S6 samples (5.0 mg 
Figure 5. Comparison of the curves describing the degradation rates of the S4 and S6 samples (5.0 mg
and 2.5 mg samples, respectively; not normalized by weight). 
and 2.5 mg samples, respectively; not normalized by weight).

For both of these samples, two maxima appear at 413 °C and 630 °C, respectively. The first ones 
For both of these samples, two maxima appear at 413 ◦ C and 630 ◦ C, respectively. The first
have  a  similar 
ones have a similar shape  (with 
shape a  shoulder 
(with before 
a shoulder the the
before peak)  and and
peak) the the
same 
samemaximum 
maximum temperatures 
temperatures at   
413 °C, suggesting the same thermal effect characterized by a beginning lower than 300 °C that could 
at 413 ◦ C, suggesting the same thermal effect characterized by a beginning lower than 300 ◦ C that
be attributed to the depolymerisation and bond breakings of epoxy‐acrylic organic binder fraction. 
could be attributed to the depolymerisation and bond breakings of epoxy-acrylic organic binder
Therefore, 
fraction. DTG  analysis 
Therefore, revealed 
DTG analysis that  thermal 
revealed behaviour 
that thermal behaviourof  epoxy‐acrylic 
of epoxy-acrylic binder 
binderis is similar, 
similar,
notwithstanding the different substituents (phenyl, instead of methyl groups). The only difference is 
notwithstanding the different substituents (phenyl, instead of methyl groups). The only difference is
the shoulder that has a different intensity is probably due to the phenyl group fraction. 
the shoulder that has a different intensity is probably due to the phenyl group fraction.
Once  again,
Once again,  the  phenyl  group
the phenyl group  seems
seems  responsible
responsible  for
for  the
the  significant
significant  temperature
temperature  differences
differences 
attributed to the oxidation of organic substituents of silicones, highlighted for the second peak: this 
attributed to the oxidation of organic substituents of silicones, highlighted for the second peak: this
appears 
appears 27 27  ◦°C  before  in
C before in  the
the S4
S4 formulation
formulation than
than in
in S6.
S6.  Thermal 
Thermal analysis 
analysis is 
is in  agreement  with
in agreement with  the
the 
literature for PDMS stability [20–24], even when considering the presence of other components inside 
literature for PDMS stability [20–24], even when considering the presence of other components inside
formulations.  The 
formulations. The temperature 
temperature difference 
difference between 
between the 
the two 
two high‐temperature 
high-temperature DTG  DTG peaks 
peaks may 
may bebe 
attributed to different organic parts, as S4 silicon resin has phenyl groups only, while S6 has methyl 
attributed to different organic parts, as S4 silicon resin has phenyl groups only, while S6 has methyl
and phenyl substituents. The introduction of phenyl substituents on silicone chains has been found 
and phenyl substituents. The introduction of phenyl substituents on silicone chains has been found
to increase the onset temperature of degradation [21,22]. According to [23], the thermal stability of 
to increase the onset temperature of degradation [21,22]. According to [23], the thermal stability
siloxane 
of siloxanepolymers 
polymersincreases 
increaseson  on
decreasing  the the
decreasing phenyl  content 
phenyl and and
content this this
trend  is  confirmed 
trend is confirmedby  our 
by
analyses (the maximum rate of the weight loss on S4 sample appears at ca. 580 °C instead of ca. 600 °C 
our analyses (the maximum rate of the weight loss on S4 sample appears at ca. 580 C instead of ◦
for the S6 sample). Analysing the thermal behaviour at higher temperatures, during polydiphenyl‐
dimethyl  siloxane  pyrolysis,  evolution  of  free  benzene  and  volatile  cyclic  siloxanes  occurs,  as 
reported  in  [20,22].  As  seen  in  Figure  4,  the  carbon  removal,  during  silicone  thermal  degradation 
appears  more  pronounced  at  the  280  °C–530  °C  weight  loss  because  of  a  decrease  in  the  phenyl 
content (a difference of 5.9%); this effect may be due both to the different steric hindrances and to the 
Coatings 2017, 7, 213 9 of 16

ca. 600 ◦ C for the S6 sample). Analysing the thermal behaviour at higher temperatures, during
polydiphenyl-dimethyl siloxane pyrolysis, evolution of free benzene and volatile cyclic siloxanes
occurs, as reported in [20,22]. As seen in Figure 4, the carbon removal, during silicone thermal
degradation appears more pronounced at the 280–530 ◦ C weight loss because of a decrease in the
phenyl content (a difference of 5.9%); this effect may be due both to the different steric hindrances
and to the layout of silicone chains due to methyl of phenyl groups [23]. Accordingly, the inspections
of residues of polydiphenyl-dimethyl siloxanes thermally degraded in air revealed a greyish white
powder constituted mainly of white silica and black silicon-oxycarbide [23,25] in which Si atoms are
simultaneously bonded to carbon and oxygen [26]. Moreover, from the elemental analysis, the weight
Coatings 2017, 7, 213  9 of 15 
percent of C concentrations inside residues has been found to be three times higher in the case of a
decreases, a more stable and protective Si–O–C layer is formed without aromatic ring interferences, 
phenyl polysiloxane with respect to a fully-methylated one [23]. Hence, as the phenyl content decreases,
with low carbon content [24]. As a conclusion, this hypothesis is in accordance with thermogravimetric 
a more stable and protective Si–O–C layer is formed without aromatic ring interferences, with low
analysis, which clearly indicates that the S6, SF1, and SF2 samples, composed by a methyl‐phenyl 
carbon content [24]. As a conclusion, this hypothesis is in accordance with thermogravimetric analysis,
silicone, show a greater weight loss than S4. Specifically, thermal analyses indicate that S4 has a lower 
which clearly indicates that the S6, SF1, and SF2 samples, composed by a methyl-phenyl silicone, show
weight 
a greaterloss  than loss
weight S6, than
in  agreement  with thermal
S4. Specifically, the  difficulty  of indicate
analyses carbon  residues’ 
that S4 hasoxidation/separation, 
a lower weight loss than as 
hypothesized above. 
S6, in agreement with the difficulty of carbon residues’ oxidation/separation, as hypothesized above.
Finally,  the S4S4 
Finally, the residue 
residue waswas  supposed 
supposed to  present 
to present high Chigh  C  content 
content and lowand  low yield.
ceramic ceramic 
Thisyield.  This 
hypothesis
hypothesis is strongly supported by the lower adhesion and stronger chalking exhibited by the S4 
is strongly supported by the lower adhesion and stronger chalking exhibited by the S4 coating with respect
to S6, as discussed above [23,24]. Moreover, the second DTG peak is about 30 ◦ C before for the phenyl
coating with respect to S6, as discussed above [23,24]. Moreover, the second DTG peak is about 30 °C 
before for the phenyl substituted silicon chain, probably meaning that the oxidized fragments are 
substituted silicon chain, probably meaning that the oxidized fragments are placed in the upper part of the
placed in the upper part of the film, in a more favourable position for chalking to occur. 
film, in a more favourable position for chalking to occur.
S6, SF1, and SF2 formulations are compared in Figure 6; the shape of the curves is the same for 
S6, SF1, and SF2 formulations are compared in Figure 6; the shape of the curves is the same for
the three coatings. From the DTG plot, reported in Figure 7, it is evident that the amount of graphene 
the three coatings. From the DTG plot, reported in Figure 7, it is evident that the amount of graphene
is not relevant as the weight losses occur at approximately the same temperatures. In comparison 
is not relevant as the weight losses occur at approximately the same temperatures. In comparison with
with graphene containing formulations, the shape of the DTG curves of S6 are almost the same as SF1 
graphene containing formulations, the shape of the DTG curves of S6 are almost the same as SF1 and
and 
SF2, SF2,  with 
with the the  exception 
exception that thethat 
ratesthe  rates  of 
of weight weight 
losses losses 
of SF1 and of 
SF2SF1  and 
(these SF2  (these 
curves curves  are 
are superimposed
superimposed  in  Figure  7),  graphene‐containing 
in Figure 7), graphene-containing formulations, occur ◦
formulations, 
15 C before occur  15 of
those °C the
before  those  of 
S6 sample, the  S6 
probably
sample, probably due to a different material thermal conductivity. 
due to a different material thermal conductivity.

 
Figure 6. Comparison of the weight losses of the S6 sample, without graphene, and the SF1 and SF2 
Figure 6. Comparison of the weight losses of the S6 sample, without graphene, and the SF1 and SF2
samples, with graphene. 
samples, with graphene.
  
Figure 6. Comparison of the weight losses of the S6 sample, without graphene, and the SF1 and SF2 
Coatings 2017, 7, 213 10 of 16
samples, with graphene. 

 
Figure 7. DTG curves of S6, SF1, and SF2 samples (not normalized). 
Figure 7. DTG curves of S6, SF1, and SF2 samples (not normalized).
Coatings 2017, 7, 213  10 of 15 

Differential scanning calorimetry (DSC) analyses for the same samples, performed until 300 ◦ C,
Differential scanning calorimetry (DSC) analyses for the same samples, performed until 300 °C, 
are reported
are  reported inin Figure 8. 8. 
Figure  The curves
The  are are 
curves  placed at different
placed  µW level
at  different  μW and have
level  a similar
and  have  a outline,
similar probably
outline, 
related to the graphene amount. In fact, SF1 and SF2 curves appear flatter mainly after 200 ◦ C, meaning
probably related to the graphene amount. In fact, SF1 and SF2 curves appear flatter mainly after 200 °C, 
a stability of the specific heat, probably related to graphene amount because of the slope of the curve,
meaning a stability of the specific heat, probably related to graphene amount because of the slope of 
decreases in the order: S6 (0% graphene) > SF2 (0.3% graphene) > SF1 (0.5% graphene).
the curve, decreases in the order: S6 (0% graphene) > SF2 (0.3% graphene) > SF1 (0.5% graphene). 

 
Figure 8. Comparison of the DSC behaviors of S6, SF1, and SF2 samples at the same weight (5 mg). 
Figure 8. Comparison of the DSC behaviors of S6, SF1, and SF2 samples at the same weight (5 mg).

3.3. Film Chemical Composition 
3.3. Film Chemical Composition
We  analysed  the  S4  and  S6  coatings  with  the  Glow  discharge  optical  emission  spectroscopy 
We analysed the S4 and S6 coatings with the Glow discharge optical emission spectroscopy
(GDOES). The difference between the two samples is the organic part of silicone binder: methyl (S4) 
(GDOES). The difference between the two samples is the organic part of silicone binder: methyl (S4)
and phenyl‐methyl (S6), respectively (Table 1). The analysis allows checking if some layering had 
and phenyl-methyl (S6), respectively (Table 1). The analysis allows checking if some layering had taken
taken  place  due  to  the  inhomogeneous  distribution  of  pigments  and  fillers  all  along  the  coating 
place due to the inhomogeneous distribution of pigments and fillers all along the coating thickness.
thickness. Results are plotted in Figures 9 and 10. 
Results are plotted in Figures 9 and 10.
1.2
S4
1.1
C 156
1.0

0.9

0.8 Ca 393
Relative Intensity

0.7
S 180
0.6

0.5 K 766
0.4
3.3. Film Chemical Composition 
We  analysed  the  S4  and  S6  coatings  with  the  Glow  discharge  optical  emission  spectroscopy 
(GDOES). The difference between the two samples is the organic part of silicone binder: methyl (S4) 
and phenyl‐methyl (S6), respectively (Table 1). The analysis allows checking if some layering had 
taken  2017,
Coatings place  due  to  the  inhomogeneous  distribution  of  pigments  and  fillers  all  along  the  coating 
7, 213 11 of 16
thickness. Results are plotted in Figures 9 and 10. 

1.2
S4
1.1
C 156
1.0

0.9

0.8 Ca 393
Relative Intensity

0.7
S 180
0.6

0.5 K 766
0.4

0.3

0.2
Al 396
0.1
Si 288 Fe 238
0.0
Mn 403
-0.1
5 10 15 20 25 30 35 40 45 50 55 60 65 70
Depth [µm]
 
Figure 9. GDOES spectra of the S4 sample. 
Coatings 2017, 7, 213  Figure 9. GDOES spectra of the S4 sample. 11 of 15 

1.2
S6
1.1
C 156
1.0

0.9 Ca 393
Relative Intensity

0.8
S 180
0.7

0.6

0.5
K 766
0.4

0.3

0.2
Al 396
0.1
Si 288 Fe 238
0.0
Mn 403
-0.1
5 10 15 20 25 30 35 40 45 50 55 60 65 70
Depth [µm]
 
Figure 10. GDOES of the S6 sample. 
Figure 10. GDOES of the S6 sample.

Firstly,  the  film  thickness  appears  properly  produced,  between  40  and  60  μm.  Moreover,  no 
Firstly, the film thickness appears properly produced, between 40 and 60 µm. Moreover, no relevant
relevant  layering  is  observed  in  both  coatings  as  the  concentration  of  all  elements  from  the  film 
layering is observed in both coatings as the concentration of all elements from the film surface to the
surface to the substrate both slightly change at the same ratio (C, Ca, S) or remain unchanged (K, Al, 
substrate both slightly change at the same ratio (C, Ca, S) or remain unchanged (K, Al, Si, Mn). The first
Si, Mn). The first group of elements is characterized by concentration gradients; C (from the binder) 
group of elements is characterized by concentration gradients; C (from the binder) and Ca appear more
and Ca appear more densely packed near the substrate, particularly in the S4 than in the S6 sample. 
densely packed near the substrate, particularly in the S4 than in the S6 sample. Otherwise, the S line,
Otherwise, the S line, related to the baryte concentration, appears more elevated both at the surface 
related to the baryte concentration, appears more elevated both at the surface and at the bottom of the
and at the bottom of the film than in the middle. Inversely, S4 and S6 analyses show that the curves 
film than in the middle. Inversely, S4 and S6 analyses show that the curves related to Mn are nearly
related to Mn are nearly horizontal, confirming the homogeneous dispersion of pigment inside the 
horizontal, confirming the homogeneous dispersion of pigment inside the coatings. Similarly, K, Si, and
coatings.  Similarly,  K,  Si,  and  Al  concentrations,  related  to  micro  mica,  appear  quite  stable.  To 
Al concentrations, related to micro mica, appear quite stable. To conclude, the comparison between S4 and
conclude, the comparison between S4 and S6 coatings indicates a greater homogeneity and lack of 
important  gradients  of  concentration,  this  is  true  of  S4  in  the  S6  composition.  For  chalking,  the 
GDOES analysis seems to confirm that it depends on the release of pigment particles or extenders 
(particularly  baryte)  after  the  thermal  degradation  of  the  binder;  no  relevant  layering  of  pigment 
and/or filler appears inside the coating to justify the difference in the chalking performance. From the 
other site, the increasing binder concentration from the surface towards the substrate, which is very 
Coatings 2017, 7, 213 12 of 16

S6 coatings indicates a greater homogeneity and lack of important gradients of concentration, this is true
Coatings 2017, 7, 213 
of S4 in the S6 composition. For chalking, the GDOES analysis seems to confirm that it depends 12 of 15 on the
Coatings 2017, 7, 213  12 of 15 
release of pigment particles or extenders (particularly baryte) after the thermal degradation of the binder;
of low steric hindrance methyl groups, allowing rearrangements of macromolecules. These domains 
no relevant layering of pigment and/or filler appears inside the coating to justify the difference in the
of low steric hindrance methyl groups, allowing rearrangements of macromolecules. These domains 
are  reinforcing  agents  and  they  can  properly  affect  properties  of  organic‐inorganic  hybrid 
chalking performance. From the other site, the increasing binder concentration from the surface towards
are  reinforcing  agents 
composites. Hence,  and 
by  heat  they  can  properly  affect 
treatment, agglomerates  may properties  of into 
be  converted  organic‐inorganic 
thermally‐stable hybrid 
silica 
the substrate, which is very pronounced in the S4 sample, could have caused a deeper degradation and
composites. Hence,  by  heat  treatment, agglomerates  may  be  converted  into  thermally‐stable  silica 
particles, enhancing substrate adhesion and film cohesiveness. Additionally, the complexity of paint 
an increase of the particle amount released at a constant concentration of all the other elements.
particles, enhancing substrate adhesion and film cohesiveness. Additionally, the complexity of paint 
formulations prevents a more precise understanding of the phenomena. In fact, as reported in [23], 
formulations prevents a more precise understanding of the phenomena. In fact, as reported in [23], 
the 
3.4. presence 
SEM Analysis of  acidic  or  basic  impurities  of  fillers  and  residual  catalysts  might  influence  the 
the  presence  of  acidic  or  basic  impurities  of  fillers  and  residual  catalysts  might  influence  the 
polysiloxane thermo‐oxidative degradation mechanism. The choice of the most performant coatings 
Coating morphology was analysed by scanning electron microscope (SEM) and energy dispersive
polysiloxane thermo‐oxidative degradation mechanism. The choice of the most performant coatings 
was,  however,  aimed  to  link  the  chalking  effect  to  the  film  surface  morphology  after  thermal 
spectroscopy
was,  however,  (EDS). S4 and
aimed  S6 SEM
to  link  micrographs,
the  chalking  before
effect  HT,film 
to  the  are reported in Figures 11 after 
surface  morphology  and 12.thermal 
degradation. 
degradation. 

 
  wollastonite  and   
Figure  11.  S4  coating;  section  before  HT.  In  the  squares:  (1,2)  densely  packed 
Figure 11. S4 coating; section before HT. In the squares: (1,2) densely packed wollastonite and (3)
Figure  11.  S4  coating;  section  before  HT.  In  the  squares:  (1,2)  densely  packed  wollastonite  and   
(3) wollastonite free region. 
wollastonite free region.
(3) wollastonite free region. 

 
 
Figure 12. S6 coating; section before HT. Homogeneous distribution of fillers. 
Figure 12. S6 coating; section before HT. Homogeneous distribution of fillers. 
Figure 12. S6 coating; section before HT. Homogeneous distribution of fillers.

The SEM micrographs of the coating section before the heat treatment help to analyse the
distribution of fillers in the film. White spots were found to be baryte, large light grey ones’,
wollastonite, and dark grey ones micro mica. By comparing the distribution of the large wollastonite
particles it appears that the filler distribution is more homogeneous in the S6 section (Figure 12). All the
particles, however, are (a) more homogeneously distributed in the S6 film than in the S4 one supporting
the chalking results; and (b) denser and not homogeneously packed in S4 sample near the substrate
surface than in the S6 one, validating the GDOES results.
Polymeric domains, with a resembling sphere geometry, were identified in the S6 and not in
the S4 coating. Images (a)  are reported in Figure 13. From EDS analysis, (b) the domains are rich of
(a)  (b)
Figure  13.  (a)  SEM‐EDS  images  at  high  magnification  of  S6  coating  before  HT.  SEM,  and  (b)  EDS 
Figure  13.  (a)  SEM‐EDS  images  at  high  magnification  of  S6  coating  before 
analysis of S6 details, highlighted by yellow circles in the SEM image.    HT.  SEM,  and  (b)  EDS 
analysis of S6 details, highlighted by yellow circles in the SEM image.   
  
Figure  11.  S4  coating;  section  before  HT.  In  the  squares:  (1,2)  densely  packed  wollastonite  and   
(3) wollastonite free region. 
Coatings 2017, 7, 213 13 of 16

silicone inside IPNs. According to [27], the uniformly dispersed dark spherical agglomerates might
be formed by condensed polyhedral oligomeric 3D siloxane structures. These may be promoted by
the presence of low steric hindrance methyl groups, allowing rearrangements of macromolecules.
These domains are reinforcing agents and they can properly affect properties of organic-inorganic
hybrid composites. Hence, by heat treatment, agglomerates may be converted into thermally-stable
silica particles, enhancing substrate adhesion and film cohesiveness. Additionally, the complexity
of paint formulations prevents a more precise understanding of the phenomena. In fact, as reported
in [23], the presence of acidic or basic impurities of fillers and residual catalysts might influence
the polysiloxane thermo-oxidative degradation mechanism. The choice of the most performant
coatings was, however, aimed to link the chalking effect to the film surface   morphology after
thermal degradation.
Figure 12. S6 coating; section before HT. Homogeneous distribution of fillers. 

(a)  (b)
Figure  13.  (a)  SEM‐EDS  images  at  high  magnification  of  S6  coating  before  HT.  SEM,  and  (b)  EDS 
Figure 13. (a) SEM-EDS images at high magnification of S6 coating before HT. SEM; and (b) EDS
analysis of S6 details, highlighted by yellow circles in the SEM image.   
analysis of S6 details, highlighted by yellow circles in the SEM image.

After 12 h at 450 ◦ C, we examined S6 and SF1 samples by SEM-EDS; the low-magnification images
are reported in Figure 14.
The two images at low magnification give a large sampling area and they clearly show large
coating failures. It is evident that SF1 has a superior resistance to chalking in comparison with the S6
sample as the integrity of the coating is preserved in the SF1 sample, but not in the S6 one. Examining
more deeply the images of Figure 14, the SF1 coating presents no delamination, blistering, and void
formation, while the S6 sample is broken in several points of the coating.
At the end of our investigation, SEM images clearly indicate a greater resistance to deformation and
breaking of the graphene containing coatings with respect to the S-type formulations. Superior properties
of polymer-graphene nanocomposites are reported in literature [9–11,13]. Moreover, during thermal
degradation of polysiloxanes, evolution of free benzene and volatile cyclic oligomers occurs [19,20,22].
According to [22], the importance of mass transfer of degradation products away from the coating
is significant and it controls the degradation process. Hence, being that graphene has low permeability
to all gases [13], it may promote the formation of a nano-structured ceramic residue, upon thermal
conversion [26], leading to higher surface integrity, as revealed in Figure 14.
during thermal degradation of polysiloxanes, evolution of free benzene and volatile cyclic oligomers 
occurs [19,20,22]. 
According  to  [22],  the  importance  of  mass  transfer  of  degradation  products  away  from  the 
coating is significant and it controls the degradation process. Hence, being that graphene has low 
Coatings 2017, 7, 213
permeability to all gases [13], it may promote the formation of a nano‐structured ceramic residue,  14 of 16

upon thermal conversion [26], leading to higher surface integrity, as revealed in Figure 14. 

(A)

(B)
Figure 14. (A) Low‐ and (B) high‐magnification images of sections after HT: (a) S6 coating section; (b) 
Figure 14. (A) Low- and (B) high-magnification images of sections after HT: (a) S6 coating section;
SF1 coating section. 
(b) SF1 coating section.

4. Conclusions 
4. Conclusions
In this paper we investigated the surface powdering after high‐temperature treatment of IPN 
In this paper we investigated the surface powdering after high-temperature treatment of IPN
silicon‐epoxide coatings. At first, the data led us to suppose that the IPN binder that is formed by two 
silicon-epoxide coatings. At first, the data led us to suppose that the IPN binder that is formed by
homopolymers  braided  to  form  a  mesh  causes  the  polymer  chains  to  be  well  organized,  without 
two homopolymers braided to form a mesh causes the polymer chains to be well organized, without
forming high‐density domains and without forming intricate arrangements, like long chains typically 
forming high-density domains and without forming intricate arrangements, like long chains typically
shaping  themselves.  Indeed,  our  results  provide  evidence  that,  after  the  treatment  at  450  ◦°C,  the 
shaping themselves. Indeed, our results provide evidence that, after the treatment at 450 C, the
organization  of  the  inorganic  part  depends  on  the  initial  layout  of  the  polymer  chain.  A  greater 
organization of the inorganic part depends on the initial layout of the polymer chain. A greater
homogeneity  develops  when  the  aromatic  (phenyl)  substituents  of  the  silicone  are  substituted  by 
homogeneity develops when the aromatic (phenyl) substituents of the silicone are substituted by
methyl  groups.  Moreover,  to  obtain  a  deeper  understanding,  graphene  was  added  because  of  its 
methyl groups. Moreover, to obtain a deeper understanding, graphene was added because of
thermal  conductivity,  which  more  homogeneously  distributes  the  temperature  gradients  inside   
its thermal conductivity, which more homogeneously distributes the temperature gradients inside
the coating. 
the coating.
The adhesion test analyses reveal that the methyl groups promote a better adhesion of the
paint residues on the metal substrate, after the treatment at 450 ◦ C/10 min of the coatings, than the
phenyl group. In a parallel manner, the powdering degree is reduced. Thermal analyses support the
previous observations and reveal that the carbon residues of the phenyl group remain longer in the
layer, with the detrimental effect. Adhesion and thermal analyses mainly refer to the macro-level
observations, while both GDOES and the electron microscope analyses substantiate at a micro-level
that a greater homogeneous distribution of fillers is obtained with graphene. The distribution of the
residue after the high-temperature treatment appears a consequence of the polymer chain layout soon
after the application. Parameters that need to be investigated further are as follows: the different
organisation induced on the silicone resins by aromatic substituents in comparison to the methyl ones,
the different organisation of the chain arrangement physically induced by graphene platelets, and,
moreover, the different organisation induced by a better heat distribution during the high-temperature
treatment. The likelihood of driving the coatings for high thermo-oxidative protection toward better
Coatings 2017, 7, 213 15 of 16

performance seems to depend on the chemical and physical control of the thermal decomposition of
the organic parts.

Acknowledgments: We acknowledge Akzo Nobel Coatings (S.P.A.), Como, CO, Italy, for the technical support
and the materials supply.
Author Contributions: Simone Giaveri performed the experiments. Paolo Gronchi contributed analysis tools,
analyzed the data, and wrote the paper. Alessandro Barzoni conceived and designed the experiments.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Bohm, S. Graphene against corrosion. Nat. Nanotechnol. 2014, 9, 741–742. [CrossRef] [PubMed]
2. Biller, K. Anticorrosion coating market to reach $31.73 bn by 2022. Focus Powder Coat. 2017, 2017, 6.
3. Dhoke, S.K.; Palraj, S.; Maruthan, K.; Selvaraj, M. Preparation and characterization of heat-resistant
interpenetrating polymer network (IPN). Prog. Org. Coat. 2007, 59, 21–27. [CrossRef]
4. Sperling, L.H.; Hu, R. Interpenetrating polymer networks. In Polymer Blends Handbook; Utacki, L.A., Wilkie, C.,
Eds.; Springer: Berlin, Germany, 2014; pp. 677–724.
5. Kumar, S.A.; Narayanan, T.S.N.S. Thermal properties of siliconized epoxy interpenetrating coatings.
Prog. Org. Coat. 2002, 45, 323–330. [CrossRef]
6. Dhoke, S.K.; Maruthan, K.; Palraj, S.; Selvaraj, M. Performance of black pigments incorporated in
interpenetrating polymer network (IPN). Prog. Org. Coat. 2006, 56, 53–58. [CrossRef]
7. Buxbaum, G. Introduction. In Industrial Inorganic Pigments, 2nd ed.; Wiley–VCH Verlag GmbH: Weinheim,
Germany, 1998.
8. Ahmad, S.; Gupta, A.P.; Sharmin, E.; Alam, M.; Pandey, S.K. Synthesis, characterization and development of
high performance siloxane-modified epoxy paints. Prog. Org. Coat. 2005, 54, 248–255. [CrossRef]
9. Kuilla, T.; Bhadra, S.; Yao, D.; Kim, N.H.; Bose, S.; Lee, J.H. Recent advances in graphene based polymer
composites. Prog. Polym. Sci. 2010, 35, 1350–1375. [CrossRef]
10. Naebe, M.; Wang, J.; Amini, A.; Khayyam, H.; Hameed, N.; Li, L.H.; Chen, Y.; Fox, B. Mechanical property
and structure of covalent functionalised graphene/epoxy nanocomposites. Sci. Rep. 2014, 4, 4375. [CrossRef]
[PubMed]
11. Tong, Y.; Bohm, S.; Song, M. Graphene based materials and their composites as coatings. Austin J. Nanomed.
Nanotechnol. 2013, 1, 1003.
12. Teng, C.; Ma, C.M.; Lu, C.; Yang, S.; Lee, S.; Hsiao, M.; Yen, M.; Chiou, K.; Lee, T. Thermal conductivity
and structure of non-covalent functionalized graphene/epoxy composites. Carbon 2011, 49, 5107–5116.
[CrossRef]
13. Potts, J.R.; Dreyer, D.R.; Bielawski, C.W.; Ruoff, R.S. Graphene-based polymer nanocomposites. Polymer
2011, 52, 5–25. [CrossRef]
14. Barletta, M.; Lusvarghi, L.; Pighetti Mantini, F.; Rubino, G. Epoxy-based thermosetting powder coatings:
Surface appearance, scratch adhesion and wear resistance. Surf. Coat. Technol. 2007, 201, 7479–7504.
[CrossRef]
15. Belder, E.G.; Rutten, H.J.J.; Perera, D.Y. Cure characterization of powder coatings. Prog. Org. Coat. 2001, 42,
142–149. [CrossRef]
16. Lee, S.S.; Han, H.Z.Y.; Hilborn, J.G.; Manson, J.E. Surface structure build-up in thermosetting powder
coatings during curing. Prog. Org. Coat. 1999, 36, 79–88. [CrossRef]
17. Giaveri, S. High Temperature Organic Powder Coatings: Characterisation and Innovations. Master’s Thesis,
Politecnico di Milano, Milan, Italy, September 2015.
18. Meng, X.; Zhang, H.; Zhu, J. Characterization of particle size evolution of the deposited layer during
electrostatic powder coating processes. Powder Technol. 2009, 195, 264–270. [CrossRef]
19. Grundke, K.; Michel, S.; Osterhold, M. Surface tension studies of additives in acrylic resin-based powder
coatings using the wilhelmy balance technique. Prog. Org. Coat. 2000, 39, 101–106. [CrossRef]
20. Camino, G.; Lomakin, S.; Lazzari, M. Polydimethylsiloxane thermal degradation Part 1. Kinetic aspects.
Polymer 2001, 42, 2395–2402. [CrossRef]
Coatings 2017, 7, 213 16 of 16

21. Mazhar, M.; Zulfiqar, M.; Piracha, A.; Ali, S.; Ahmed, A. Comparative thermal stability of homopolysiloxanes
and copolysiloxanes of dimethyl/diphenyl silanes. J. Chem. Soc. Pak. 1990, 12, 225–229.
22. Deshpande, G.; Rezac, M.E. The effect of phenyl content on the degradation of poly (dimethyl diphenyl)
siloxane copolymers. Polym. Degrad. Stab. 2001, 74, 363–370. [CrossRef]
23. Deshpande, G.; Rezac, M.E. Kinetic aspects of the thermal degradation of poly (dimethyl siloxane) and poly
(dimethyl diphenyl siloxane). Polym. Degrad. Stab. 2002, 76, 17–24. [CrossRef]
24. Zhou, W.; Yang, H.; Guo, X.; Lu, J. Thermal degradation behaviours of some branched and linear
polysiloxanes. Polym. Degrad. Stab. 2006, 91, 1471–1475. [CrossRef]
25. Narisawa, M. Silicone resin applications for ceramic precursors and composites. Materials 2010, 3, 3518–3536.
[CrossRef]
26. Bernardo, E.; Fiocco, L.; Parcianello, G.; Storti, E.; Colombo, P. Advanced ceramics from preceramic polymers
modified at the nano-scale: A review. Materials 2014, 7, 1927–1956. [CrossRef] [PubMed]
27. Pantano, C.G.; Singh, A.K.; Zhang, H. Silicon oxycarbide glasses. J. Sol-Gel Sci. Technol. 1999, 14, 7–25.
[CrossRef]

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