processes

Article
Comparative Study of the Performances of Al(OH)3
and BaSO4 in Ultrafine Powder Coatings
Weihong Li 1 , Diego Cárdenas Franco 2 , Marshall Shuai Yang 2 , Xinping Zhu 3 ,
Haiping Zhang 1 , Yuanyuan Shao 1 , Hui Zhang 1,2, * and Jingxu Zhu 1,2
1 Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical
Engineering and Technology, Tianjin University, Tianjin 300072, China; weihli@tju.edu.cn (W.L.);
hpzhang@tju.edu.cn (H.Z.); yshao@tju.edu.cn (Y.S.); jzhu@uwo.ca (J.Z.)
2 Particle Technology Research Center, Department of Chemical & Biochemical Engineering, The University of
Western Ontario, London, ON N6A 5B9, Canada; cardenas_franco@yahoo.ca (D.C.F.);
marshall.yang@uwo.ca (M.S.Y.)
3 Wesdon-Rivers Institute of Powder Coatings Science and Technology, Zhaoqing 526000, China;
xzhu269@gmail.com
* Correspondence: hzhang1@tju.edu.cn; Tel.: +86-222-349-7607




Received: 7 May 2019; Accepted: 23 May 2019; Published: 27 May 2019


Abstract: Ultrafine powder coatings are one of the development directions in the powder coating
industry, as they can achieve thin coatings with good leveling and high surface smoothness comparable
to liquid coatings. Compared to regular coatings, they experience a higher sensitivity to any
incompatibilities, e.g., filler from coating components. The properties of fillers play a great role in the
performance of coating films. Aluminum trihydrate (Al(OH)3 ) is a well-known filler in solvent-based
coatings and other polymer industries. To study and evaluate the performances of Al(OH)3 in
ultrafine powder coatings, a popular filler, barium sulfate (BaSO4 ) is used for comparison. Both
fillers are added in ultrafine powder coatings based on two of the most commonly used resin systems
(polyester-epoxy and polyester). The differences of physical and chemical properties between both
fillers have significant influences on several properties of powder paints and coating films. The polar
groups (hydrogen bond) in Al(OH)3 result in the strong interaction between inorganic filler and
organic polymer matrix, thus decreasing the molecular network mobility and influencing the chain
formation, which is verified by differential scanning calorimetric (DSC). The bed expansion ratio
(BERs) of powder paints incorporated with Al(OH)3 are much higher than those with BaSO4 , which
indicate more uniform gas-solid contact during the spraying process. Samples with Al(OH)3 exhibit
much lower specular gloss at 60◦ , which are expected to achieve remarkable matting effects. Superior
corrosion resistances can be observed for almost all the coated panels incorporated with Al(OH)3 in
contrast to those with BaSO4 . Other aspects are slightly influenced by the difference between the
two fillers, such as the angle of repose values (AORs) of powder paints, the impact resistance and
flexibility of coating films.

Keywords: Al(OH)3 ; BaSO4 ; filler; ultrafine powder coatings

1. Introduction
During the last few decades, engineers and researchers have attached great importance to
powder coatings due to their economic and environmental benefits. Compared with solvent-borne
coatings, they eliminate the use of volatile organic compounds (VOC) that are both expensive and
environmentally unfriendly. Moreover, the overspray paint powders can be reclaimed and reused,
resulting in a nearly 100% transfer efficiency [1,2]. However, the particle sizes of regular powder

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Processes 2019, 7, 316 2 of 19

coating are generally in the range from 30µm to 60µm, which leads to a thicker film with rougher
appearance in comparison with solvent-borne coatings.
Recently, there has been a strong trend to reduce the particle size to improve the surface quality of
the final coatings and lead to the considerable cost savings of material and energy [2–7]. Therefore,
ultrafine powder coatings (D50 < 25 µm) have attracted more and more attention from the finishing
industries, such as oral drug delivery systems, dental and orthopedic implants and the pharmaceutical
industry [8–10]. In contrast to regular powder coatings (D50 > 30 µm), the ultrafine powder coatings are
with a higher sensitivity to any incompatibilities from coating components and application environment
due to their smaller mean particle size, poorer flowability and the thinner film they can form [1,2,7].
Considering their potential utilization and sensitivity, study on the effects of coating components, e.g.
fillers on their performance, is more valuable compared to the regular powder coatings. By including
fillers in the ultrafine powder coatings, the agglomerates formed may cause a decrease in its flowability
as well as defects during spraying and curing process [2,7,11]. Therefore, the study of the effects of
filler addition on the performance of the ultrafine powder is of great significance.
Fillers are one of five principal components of powder coatings that include polymer resins, curing
agents (also called hardeners or cross-linkers), pigments and additives. They are usually inorganic
substances with chemical stability and are produced artificially or naturally like minerals. Fillers
have two functions in coatings: one is to reduce costs by decreasing the dosage of the polymer resin,
normally the main-cost part in the formulation; the other is to modify certain physical, chemical or
visual properties of the coating [12–16]. The commonly used fillers in powder coatings include blanc
fixe (BaSO4 ), lithopone (ZnS·BaSO4 ), talc (Mg3 Si4 O10 (OH)2 ), zinc white (ZnO) and carbon black (C),
etc. [17–22]. Above all, BaSO4 is used in a high percentage of powder paints because of its electric
conductivity and light transparency in thin coatings.
Al(OH)3 is an extensively used filler in liquid coatings, and its usage in the polymer industry has
been reported [23–26]. Owing to its higher thermal conductivity, it can be used in room temperature
vulcanized (RTV) silicone rubber coatings for the improvement of tracking and corrosion resistances [27].
Several researchers and Al(OH)3 suppliers have also noted the superiority of Al(OH)3 in improving
the mechanical and other properties of powder coatings [28–30]. However, little systematic research is
so far reported on the comparisons of the effects of Al(OH)3 and BaSO4 on the physical properties,
ultraviolet (UV) and corrosion resistances in powder coatings.
In this study, Al(OH)3 and BaSO4 were compared as fillers in the most widely used polyester-epoxy
(hybrid) and polyester ultrafine powder coatings. The paper investigated the effects of Al(OH)3 as well
as BaSO4 on flowability of powder coatings, mechanical and other physical properties of coating films,
plus their performances under corrosive environments and other external circumstances. In addition,
the results were discussed regarding the difference of physical and chemical properties between
both fillers.

2. Experimental

2.1. Preparation and Characterization of Powder Paints

As described earlier, powder coatings consist of five principal components, including polymer
resins, curing agents, pigments, additives and fillers. The materials used in this study are shown in
Table 1. In this research, four different filler contents were tested in two widely used resin systems.
Each sample contains different type and content of resins and curing agents, as shown in Table 2.
To determine the effects of type and content of fillers, the other components (pigments, degassing
agents and flow agents) remained constant. Physical properties of fillers incorporated in the coatings
are shown in Table 3.
Processes 2019, 7, 316 3 of 19

Table 1. Materials.

Components Hybrid (Polyester-Epoxy) Polyester

Resin Crylcoat 2440-2 Crylcoat 2440-2
Curing agent DER 663U TGIC/Araldite PT 810
Al(OH)3 /Custom Grinders Polyfill 301
Filler
BaSO4 /Sparwite W-10
Pigment Carbon black/Raven 5000 Ultra II
Degassing agent Benzoin/S602
Flow agent Acrylic polymer/Lanco P10
Fluidization additive SiO2 /AEROSIL R972
Hybrid (polyester: epoxy = 7:3 wt.%).

Table 2. Formulations of powder paints.

Contents/(wt.%)
Specimen Resin Type Filler
Resin + Curing Agent Filler Others
H-C - 97.6 0
H-A1/H-B1 80.3 17.3
Hybrid
H-A2/H-B2 Al(OH)3 /BaSO4 70 30.6
H-A3/H-B3 57.4 40.2 2.4
PE-C - 97.6 0
PE-A1/PE-B1 80.3 17.3
Polyester
PE-A2/PE-B2 Al(OH)3 /BaSO4 70 30.6
PE-A3/PE-B3 57.4 40.2
Others: pigment 1.4 wt.%, degassing agent 0.3 wt.%, flow agent 0.7 wt.%.

Table 3. Physical properties of fillers used in the study.

Median Particle Specific Refractive Oil Absorption/

Filler Shape Color
Size D50 /(µm) Gravity/(-) Index/(-) (g oil/100 g)
BaSO4 Aggregates 2.1 4.4 White 1.64 10
Al(OH)3 Irregular 9 2.4 White 1.58 28

As illustrated in Figure 1, the appropriate materials were premixed and then extruded by a
twin-screw extruder (SLJ-10, Donghui Powder Coating Processing Equipment Co., Ltd., Yantai, China).
The hot extrudates were cooled, crushed into small chips and added into an air classifier mill (ACM-02,
Donghui Powder Coating Processing Equipment Co., Ltd., Yantai, China) for fine grinding, classifying
and screening. The median particle size (D50 ) of paint powders was within the range of 18 µm ±
0.5 µm, as shown in Table 4, which was measured by a laser particle size analyzer (BT2000B, Bettersize
instruments Ltd., Dandong, China). Microstructure and morphology of the powder paints and coating
films were characterized with scanning electron microscopy (SEM, S4800, Hitachi High-Technologies
Global, Tokyo, Japan). Differential scanning calorimetric (DSC) was used to determine the glass
transition temperature (Tg ) of coatings and ∆Hcrosslinking of the crosslinking events. The DSC curves
were obtained by a calorimeter (DSC-3, Mettler Toledo Inc., Greifensee, Switzerland) at temperatures
between 25 ◦ C and 210 ◦ C. It was operated at a heating rate of 10 ◦ C/min under inert nitrogen
atmosphere (N2 ) with a flow rate of 50 mL/min.
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Filler
Resin

Curing agent Pigment

Additive
Premix
Spraying
Extrusion

Powder
Colling & Chipping paints

Grinding,
classifying &
screening

Figure
Figure 1. Schematic diagram
1. Schematic diagram of
of the
the manufacturing
manufacturing process
process of
of powder
powder coating.
coating.
Table 4. Particle size of powder paints.
Table 4. Particle size of powder paints.
Particle Size/(µm) Particle Size/(µm)
Specimen Particle Size/(μm) Specimen Particle Size/(μm)
Specimen D10 D50 D90 Specimen D10 D50 D90
D10 D50 D90 D10 D50 D90
H-C
H-C 5.77
5.77 18.02
18.02 60.02
60.02 H-C
H-C 5.77
5.77 18.02
18.02 60.02
60.02
H-A1 5.29 18.29 60.71 H-B1 5.49 18.11 59.64
H-A1 5.29 18.29 60.71 H-B1 5.49 18.11 59.64
H-A2 5.12 18.40 60.14 H-B2 5.71 18.18 60.6
H-A2
H-A3 5.12
5.48 18.40
18.10 60.14
58.33 H-B2
H-B3 5.71
5.68 18.18
17.79 60.6
59.01
H-A3
PE-C 5.48
5.29 18.10
17.82 58.33
59.64 H-B3
PE-C 5.68
5.29 17.79
17.82 59.01
59.64
PE-C
PE-A1 5.29
5.30 17.82
18.54 59.64
59.99 PE-C
PE-B1 5.29
5.51 17.82
18.24 59.64
59.70
PE-A2
PE-A1 5.91
5.30 18.04
18.54 58.64
59.99 PE-B2
PE-B1 5.79
5.51 18.13
18.24 59.17
59.70
PE-A3 5.83 17.71 56.79 PE-B3 5.66 18.10 58.96
PE-A2 5.91 18.04 58.64 PE-B2 5.79 18.13 59.17
PE-A3 5.83 17.71 56.79 PE-B3 5.66 18.10 58.96
According to Geldart’s Powder Classification, the ultrafine powder paints used in this study can
be categorized
Accordingin toGroup C (particle
Geldart’s Powdersize under 25 µm–30
Classification, µm), which
the ultrafine powder is difficult to fluidize
paints used due tocan
in this study its
cohesive naturein[31].
be categorized GroupTheCcohesion
(particleissize
attributed
under 25toµthe m–30 relatively largerisinterparticle
µ m), which attractive
difficult to fluidize dueforces,
to its
which
cohesive cannature
be overcome
[31]. The bycohesion
the addition of nanoparticles
is attributed (fluidization
to the relatively largeradditives),
interparticle thus improving
attractive the
forces,
flowability of Group C particles [32–35]. Fluidization additive used in
which can be overcome by the addition of nanoparticles (fluidization additives), thus improving thethis study is listed in Table 1,
which is dryofblended
flowability Group C (0.7 wt.%) before
particles [32–35].theFluidization
powder paints are applied
additive used inontothisthe substrates.
study is listed in Table 1,
which Flow behavior
is dry blended of (0.7
powderwt.%) paints was
before characterized
the powder paints withare
angle of repose
applied onto (AOR) and bed expansion
the substrates.
ratio Flow
(BER) behavior
tests [36]. ofAspowder
shown inpaints
Figurewas2, AOR is defined as
characterized withthe angle
angle between
of reposethe(AOR) horizontal
and and
bed
the side of the
expansion ratiocone when
(BER) the[36].
tests powder falls freely
As shown on the 2,
in Figure plate.
AOR It reflects
is defined the as
cohesiveness and internal
the angle between the
horizontal
friction of a and
powder the and
sideisof the coneemployed
commonly when thetopowdercharacterize fallsthefreely
flow on the plate.
behavior of powderIt reflects the
samples.
In general, powder
cohesiveness samplesfriction
and internal with AOR of aover
powder ◦
45 are andusually considered
is commonly cohesive,
employed while samples
to characterize thewith
flow a
behaviorAOR
smaller of powder samples.
have better In general,
flowability [37].powder samples with AOR over 45° are usually considered
BER is
cohesive, a useful
while parameter
samples with that indicates
a smaller AOR thehave
extent to which
better powders
flowability expand at a specific superficial
[37].
BER is It
gas velocity. a is
useful parameter
the ratio of the bedthat indicates
height the extent
at operating to which
conditions powderstoexpand
(expanded) the fixedatbed a specific
height,
superficial
as defined in gasEquation
velocity. (1).
It is Generally,
the ratio ofBER
the bed height
is used to at operating conditions
characterize fluidization (expanded)
quality based to theonfixed
the
bed height,
belief as defined
that a higher BER in Equation
indicates (1). Generally,
a better BER is[38].
gas-solid contact usedAto characterize
higher fluidization
BER implies quality
a large amount
based
of gas on the belief
trapped among thatthe
a higher BER indicates
paint powders, whicha contributes
better gas-solid contact [38].
to adequate A higher
gas-solid contactBERduring
implies thea
large amount
following of gas
spraying trapped
process, amonginthe
resulting paint powders,
a smoother which contributes
visual appearance. to adequate
In this study, fluidizationgas-solid
of the
contact
paint duringwas
powders the conducted
following spraying process,
in a homemade resulting
fluidized bedinasa schematically
smoother visual shownappearance.
in Figure In this
3. The
study, fluidization
fluidized bed columnofwas themadepaint powdersthat
of Plexiglas waswas conducted
75 cm tall inwith a I.D.
homemade
of 5 cm. The fluidized
expanded bedbed as
schematically
height shown in
was measured Figure 3. The fluidized
simultaneously when thebed column
paint powderswas were
madefluidized
of Plexiglas that was
steadily 75 cm
at each settall
of
with I.D. ofgas
superficial 5 cm. The expanded
velocity. bed the
In this study, height
BERwas measured
is reported simultaneously
using a gas velocity when the paint
ranging from 0powders
cm/s to
were1.0
near fluidized steadily
cm/s, which at each set of superficial
is representative fluidization gas
in velocity.
a powderIncoating
this study, the BER
process [1,39]. is reported using
a gas velocity ranging from 0 cm/s to near 1.0 cm/s, which is representative fluidization in a powder
coating process [1,39].
Processes 2019, 7, 316 5 of 19
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Hexpanded bed
BER H=Hexpanded
expanded bed
bed (1)
BER==
BER Hfixed bed (1)
(1)
H
Hfixed
fixedbed
bed
The specific gravity is a significant parameter for calculating the cost benefit of powder coatings,
The specific
The specificgravity
gravity is
is aa significant
significant parameter
parameter forfor calculating
calculating the
the cost
cost benefit
benefit of
of powder coatings,
usually in the form of square meters/kg powder coating in a given film thickness. It can provide
usuallyininthe
usually the form
form of square
of square meters/kg
meters/kg powderpowder
coatingcoating in afilm
in a given given film thickness.
thickness. It can
It can provide provide
theoretical
theoretical usage and coverage of powder coatings.
theoretical
usage usage and
and coverage of coverage of powder coatings.
powder coatings.

Figure 2. Schematic diagram of AOR measurement.

Figure 2. Schematic
Figure2. Schematic diagram
diagram of
of AOR
AOR measurement.
measurement.

Figure 3. Schematic diagram of fluidized bed.

Figure 3. Schematic
Figure3. Schematic diagram
diagram of
of fluidized
fluidizedbed.
bed.

InIn
this study,
this allall
study, thethe
powder
powder paints were
paints fabricated
were byby
fabricated anan
ACM.
ACM. The operating
The operating parameters
parametersareare
In this study, all the powder paints were fabricated by an ACM. The operating parameters are
virtually
virtuallythe
thesame,
same,with
withminor
minoradjustments
adjustmentstotoensure
ensureall
allthe
thepaint
paintsamples’
samples’ DD50 in the
50 fall in the range
rangeof
of18
virtually the same, with minor adjustments to ensure all the paint samples’ D50 fall in the range of 18
m ±±0.5
18µµm 0.5 µµm
m and are in the the same
same particle
particleshape.
shape.Consequently,
Consequently,the thedifferences
differencesofofAORs
AORs and BERs
and BERs
µ m ± 0.5 µ m and are in the same particle shape. Consequently, the differences of AORs and BERs
caused
caused bybyparticle size
particle and
size and shape cancan
shape be be
neglected.
neglected.The
The characterizations mentioned
characterizations mentioned above
abovewere
were
caused by particle size and shape can be neglected. The characterizations mentioned above were
performed by devices and instruments listed in Table
performed by devices and instruments listed in Table 5. 5.
performed by devices and instruments listed in Table 5.
Table 5. Measurements of powder paints and coating films.

Measurements Apparatuses ASTM Standards

Powder paints
PT-X (Hosokowa Micron Corporation, Hirakata,
AOR -
Japan)
Volumetric flask
Specific gravity D5965-02 (2013)
Balance (XSE105DU, Mettler Toledo Inc.,
Greifensee, Switzerland)
BER Homemade fluidized bed -
Processes 2019, 7, 316 6 of 19

Table 5. Cont.

Measurements Apparatuses ASTM Standards

Coating films
PH5800 (BYK Additives & Instruments Ltd.,
Pencil scratch hardness D3363-05 (2011)
Wesel, Germany)
Surface roughness SJ-210 (Mitutoyo Co., Kanagawa, Japan) D4417-2014
QCJ 120 (HANYI instruments Co. Ltd.,
Impact resistance D2794-93 (2010)
Wuhan, China)
BYK 5750 (BYK Additives & Instruments Ltd.,
Flexibility D522M-13
Wesel, Germany)
IQ206085 (Rhopoint Components Ltd., East
Specular gloss D523-14 (2018)
Grinstead, UK)
MX-9204 (Associated Environmental Systems
Salt spray test B117-2011, D1654-08 (2016)
Ltd., Hong Kong)
XE-3 (Q-Lab Corporation Ltd., Cleveland,
UV accelerated test G155-2013, D523-14 (2018)
OH, USA)

2.2. Preparation and Characterization of Finished Films

After measurements of powder paints described before, each of the powder samples was sprayed
on two different types of panels from Q-Lab (Q-Lab Corporation Ltd., Westlake, OH, USA): aluminum
panel (88.9/63.5/0.8, L/W/T, mm) and steel panel (127.0/76.2/0.8, L/W/T, mm). All panels were degreased
with acetone prior to spraying. Powder samples were sprayed using a Sure coat corona gun (Nordson
Corporation, Westlake, OH, USA). All the sprayed panels were cured at 204 ◦ C for 10 min to ensure
complete curing. After curing, a film thickness of 38 µm ± 5% were retained for all the subsequent
measurements. The thickness of the coating film was measured by a PosiTector 6000 thickness gage
(DeFelsko Corporation, Ogdensburg, NY, USA).
The performance of coating films depends on many factors; for instance, the properties of the
resin systems, environment exposed and other factors. Many test methods for developing and
monitoring film properties are available to simulate the application conditions and accelerate the
degradation process of powder coatings. In this study, for evaluating the pencil scratch hardness,
impact resistance, conical mandrel bend test, specular gloss, UV and corrosion resistances of the film
surface by instrumental measurements, detailed evaluation procedures are followed according to
appropriate ASTM standards. Characterizations of the coating films were conducted 24 h after cured.
Instruments used and ASTM standards followed in the measurements are presented in Table 5.
Pencil scratch hardness test uses constant pressure and special pencils (from 9H to 9B degrees) to
scratch the finished film to determine the hardness of the film. The Impact resistances of the coated
films were characterized by an impact tester. A steel weight with a hemispherical head (diameter: 13
mm, weight: 1.8 kg) was dropped from a height between 20 and 120 cm onto the coated panels. The
same procedure is repeated by increasing the height by 25 mm increments until cracks appear, which
presents the failure of the coating. Flexibility of the coating films is measured by a conical mandrel bend
apparatus. The panels are bent for about 135◦ . The radius of the cone varies from 1.5 mm to 19 mm.
The coating film is deemed flexible if no crack appears. Specular gloss describes the power of a test
surface to reflect light specularly. A complete specular light reflection is 100, while a complete diffuse
reflection is 0. The surface roughness test is conducted to characterize the discontinuities over some
distance (15 mm in this study) on the specimen surface. To ensure the reliability and reproducibility of
the test results, the measurements were performed in three different regions for each of the finished
films. The salt spray test is an essential method to evaluate corrosion resistance of a coating film
in terms of loss of adhesion under long-term exposure to salt fog. An X-form-scribe was made on
the surface of the coated panel leaving the metal substrate exposed. The representative mean rust
creepages can be determined by a rating grade from 10 to 1 (Table 6). The resistance of a powder coated
film against UV exposure (UV accelerate test) is one of the most important parameters to determine
Processes 2019, 7, x FOR PEER REVIEW 7 of 19

conditions. The measured specular gloss at 60° was used to calculate the gloss retention of the coating
Processes 2019, 7, 316 7 of 19
film. The gloss retention is defined as:
Glosst=x
Gloss retention = (2)
the applicability of a particular coating for external conditions.
Glosst=0 The UV tester used in this study is
equipped with two xenon-arc lamps with a maximum wavelength of 340 nm. A cycle consists of 102
min of UV irradiation (0.35 W/m 2 , 63 ◦ C) in dry conditions and 18 min in water spray conditions. The
Table 6. Rating number of failures at scribe.
◦
measured specular gloss at 60 was used to calculate the gloss retention of the coating film. The gloss
retention is defined as: Mean Rust Creepage/(mm) Rating Number
Zero Glosst=x 10
Gloss retention = (2)
0 to 0.5 Glosst=0 9
0.5 to 1.0 8
Table 6.1.0 to 2.0number of failures at scribe.
Rating 7
2.0 to 3.0 6
Mean Rust 3.0
Creepage/(mm)
to 5.0 Rating 5 Number
5.0
Zero to 7.0 410
07.0
to to
0.510.0 39
10.0
0.5 toto1.013.0 28
1.0
13.0toto2.016.0 17
2.0 to 3.0
>16.0 06
3.0 to 5.0 5
5.0 to 7.0 4
3. Results
7.0 to 10.0 3
10.0 to 13.0 2
3.1. Flow Behavior and Specific Gravity of to
13.0 Paint
16.0Powders 1
>16.0 0
Flow behaviors of the powder paints were characterized by AOR and BER measurements.
Figure 4 shows the AORs of the powder samples dry-blended with fluidization additives with respect
3. the
to Results
fillers’ types and contents. It is clear that the type of resin system affects the AORs of the paint
samples. AORs of the samples based on polyester are much higher than that of the hybrid. However,
3.1. Flow Behavior and Specific Gravity of Paint Powders
for the same resin system, the type of filler only makes a small difference in AOR, if the same amount
Flow behaviors
of Al(OH) 3 and BaSO of 4the powder
are used. paints were characterized
As mentioned before, theby particle
AOR andsize BERdistribution,
measurements. Figure
shape and4
shows theofAORs
humidity powder of the powder
samples cansamples
be ignoreddry-blended
because ofwith fluidization
the same additives
manufacturing with respect
processes, to the
operating
fillers’ typesand
parameters andconditions,
contents. Itas is shown
clear thatin the type5.ofThe
Figure resin system
slightly affectsAORs
higher the AORs of the paint
of samples samples.
with BaSO 4 is

AORs of due
partially the samples based
to its smaller D50on
, aspolyester
shown inare much
Table higherresults
3, which than that of the tendency
in a larger hybrid. However, for the
to the formation
same
of resin system,
agglomerates andthepoortype of filler in
dispersion only makespaints.
powder a small difference in AOR, if the same amount of
Al(OH)From3 and BaSO
our prior are used. As mentioned
4 paper and industrial experience,before, the particle
when AORssize distribution,
are higher shape and the
than 42°, humidity
paint
of powdertend
powders samples can be ignored
to agglomerate andbecause of the same
thus exhibit poor manufacturing
flowability during processes, operating
the spraying parameters
process [40].
and conditions,
Accordingly, theas shown
filler in Figure
contents 5. study
in this The slightly higher
for Al(OH) AORs
3 and BaSO of4 samples
are quitewith BaSO4 for
acceptable is partially
hybrid-
due tocoatings
based its smallerwithD50 , asaddition
the shown in of Table 3, which
fluidization results in
additives; thea AORs
larger tendency
of most oftothe
thepaint
formation
samplesof
agglomerates
vary below 42°, and poorfor
except dispersion
those based in powder paints.resins.
on polyester

48
H-A H-B
PE-A PE-B
46

44

42
AOR/ (°)

40

38

36

34

32
0 17.3 30.6 40.2
Filler contents/ (wt%)

AORs of samples.
Figure 4. AORs
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19

H-A3 H-B3

PE-A3 PE-B3
Figure 5. SEM micrographs of powder paints.
Figure 5. SEM micrographs of powder paints.
From our prior paper and industrial experience, when AORs are higher than 42◦ , the paint powders
tend to BER was used to
agglomerate andcharacterize
thus exhibit flow behavior
poor basedduring
flowability on thethebelief that a higher
spraying processBER[40].indicates more
Accordingly,
gas in the interstitial void among particles, implying more uniform gas-solid
the filler contents in this study for Al(OH)3 and BaSO4 are quite acceptable for hybrid-based coatings contact and thus better
flow the
with behavior
addition andoffluidization
fluidizationquality.
additives;Figurethe 6AORs
presents the result
of most of theof BERsamples
paint measured varyfrom samples
below 42◦ ,
based on hybrid and polyester. Evidently,
except for those based on polyester resins. filler-free powder paints exhibit the highest BERs in almost
the whole
BER wasrange of to
used superficial gas velocity.
characterize flow behaviorWith based
the increase
on theof fillerthat
belief contents, BERs
a higher BERofindicates
powder paints
more
deteriorate
gas and decrease
in the interstitial to about
void among 1.8 andimplying
particles, 1.7 for samples of H-B3
more uniform and PE-B3,
gas-solid respectively.
contact From
and thus better
previous investigations, the BERs for regular powder coatings (D 50 >30μm) showed a maximum value
flow behavior and fluidization quality. Figure 6 presents the result of BER measured from samples
of 1.6 on
based when the superficial
hybrid and polyester.gas Evidently,
velocity was 1.0 cm/s
filler-free [1]. Compared
powder paints exhibitto regular powder
the highest coatings,
BERs the
in almost
ultrafines
the normally
whole range exhibit poorer
of superficial flowabilities,
gas velocity. With the such as lower
increase BER contents,
of filler and higher BERsAOR, becausepaints
of powder of the
stronger inter-particle forces [32–36], while with the aid of the fluidization
deteriorate and decrease to about 1.8 and 1.7 for samples of H-B3 and PE-B3, respectively. From additives the BERs of the
ultrafine powder coatings in this research vary from 1.7 to 2.4 at a similar superficial gas velocity of
previous investigations, the BERs for regular powder coatings (D50 >30µm) showed a maximum value
0.93
of 1.6cm/s
when(Figure 7). A higher
the superficial BER leads
gas velocity wasto 1.0
a better gas-solid
cm/s [1]. Comparedcontact, which results
to regular powder incoatings,
a better film
the
appearance and gas saving in the electrostatic spraying process.
ultrafines normally exhibit poorer flowabilities, such as lower BER and higher AOR, because of the
strongerBesides, PE-powders
inter-particle forcesare much while
[32–36], sensitive
withtothefiller’s
aid ofincorporation,
the fluidization BERs of polyester
additives the BERs powders
of the
decrease more significantly in contrast to those of hybrid. With the increase of filler contents, the
ultrafine powder coatings in this research vary from 1.7 to 2.4 at a similar superficial gas velocity of
BERscm/s
0.93 of PE-B and7).
(Figure PE-A deteriorate
A higher very fast
BER leads to a and decrease
better gas-solid by contact,
more than 30% results
which and 20% in in contrast
a better to
film
that of PE-C, while the reduction of the BERs of H-B and H-A are 19% and 10%, respectively.
appearance and gas saving in the electrostatic spraying process.
Figure 8 shows the specific gravities of paint powders respect to different contents of two fillers.
Besides, PE-powders are much sensitive to filler’s incorporation, BERs of polyester powders
It is observed that all samples possess similar specific gravities of 1.2 when no filler is incorporated.
decrease more significantly in contrast to those of hybrid. With the increase of filler contents, the BERs
Obviously, the addition of fillers into the powder coatings directly raise its specific gravity and the
of PE-B and PE-A deteriorate very fast and decrease by more than 30% and 20% in contrast to that of
samples with the same filler contents have close values. The overall density of samples incorporated
PE-C, while the reduction of the BERs of H-B and H-A are 19% and 10%, respectively.
with BaSO4 is much higher than that of Al(OH)3, which is due to the difference of specific densities
Figure 8 shows the specific gravities of paint powders respect to different contents of two fillers.
between the two fillers.
It is observed that all samples possess similar specific gravities of 1.2 when no filler is incorporated.
Processes 2019, 7, 316 9 of 19

Obviously, the addition of fillers into the powder coatings directly raise its specific gravity and the
samples with the same filler contents have close values. The overall density of samples incorporated
Processes
with 2019, 7, x FOR PEER
BaSO REVIEW 9 of 19
Processes 2019,4 7,isxmuch higher
FOR PEER than that of Al(OH)3 , which is due to the difference of specific densities
REVIEW 9 of 19
between the two fillers.
2.6
2.6 2.6
2.6
2.6 H-C
H-C 2.6 PE-C
PE-C
H-A1
H-C
H-A1 PE-A1
PE-C
PE-A1
2.4
2.4 H-A2 2.4
2.4 PE-A2
H-A1
H-A2 PE-A1
PE-A2
2.4 H-A3
H-A2
H-A3 2.4 PE-A3
PE-A2
PE-A3
2.2 H-B1
H-A3
H-B1 2.2 PE-B1
PE-A3
PE-B1
2.2 2.2
H-B2
H-B1
H-B2 PE-B2
PE-B1
2.2 2.2 PE-B2
H-B3
H-B2
H-B3 PE-B3
PE-B2
PE-B3
2.0
2.0 H-B3 2.0
2.0 PE-B3

(-)
2.0

(-)(-)
2.0
(-)
(-) (-)

BER/
BER/
1.8
BER/

1.8 1.8
BER/

1.8

BER/
1.8
BER/

1.8
1.6
1.6 1.6
1.6
1.6 1.6
1.4
1.4 1.4
1.4
1.4 1.4
1.2
1.2 1.2
1.2
1.2 1.2
1.0
1.0 1.0
1.0
0.0
1.00.0 0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 1.0
1.0 0.0
1.00.0 0.2
0.2 0.4
0.4 0.6
0.6 0.8
0.8 1.0
1.0
0.0 0.2 0.4 gas velocity/
Superficial 0.6 (cm/s) 0.8 1.0 0.0 0.2 0.4 gas
Superficial 0.6 (cm/s)
gas velocity/
velocity/ (cm/s) 0.8 1.0
Superficial gas velocity/ (cm/s) Superficial
Superficial gas velocity/ (cm/s) Superficial gas velocity/ (cm/s)

Figure 6. Bed
Bed expansion
expansion ratios
ratios (BERs)
(BERs) of samples respect to superficial gas velocity.
velocity.
Figure 6. Bed expansion ratios (BERs) of samples respect to superficial gas velocity.
2.6
2.6
2.6 H-A
H-A H-B
H-B PE-A
PE-A PE-B
PE-B
2.5
2.5 H-A H-B PE-A PE-B
2.5
2.4
2.4
2.4
2.3
2.3
2.3
2.2
2.2
(-)
(-)(-)

2.2
BER/

2.1
BER/

2.1
BER/

2.1
2.0
2.0
2.0
1.9
1.9
1.9
1.8
1.8
1.8
1.7
1.7
1.7
1.6
1.6
1.6 00 17.3
17.3 30.6
30.6 42
42
0 Filler 17.3
contents/ (wt%)30.6 42
Filler contents/ (wt%)
Figure 7.
Figure 7. BERs
BERs of
of samples
samples at
at gas
gas velocity
velocity of
of 0.93
0.93 cm/s.
cm/s.
Figure 7. BERs of samples at gas velocity of 0.93 cm/s.
1.8
1.8
1.8 H-A
H-A H-B
H-B
H-A
PE-A
PE-A H-B
PE-B
PE-B
1.7
1.7 PE-A PE-B
1.7
(-)
(-)(-)

1.6
1.6
gravity/
gravity/

1.6
gravity/

1.5
1.5
Specific

1.5
Specific
Specific

1.4
1.4
1.4

1.3
1.3
1.3

1.2
1.2
1.2 00 17.3
17.3 30.6
30.6 40.2
40.2
0 17.3 30.6 40.2
Filler contents/ (wt%)
Filler contents/ (wt%)
Figure 8.
Figure 8. Specific gravities of
of samples.
samples.
Figure 8. Specific gravities of samples.

3.2. Physical Properties, UV and Corrosion Resistances of Coating Films

3.2. Physical Properties, UV and Corrosion Resistances of Coating Films
3.2.1. Physical Properties
3.2.1. Physical Properties
Surface hardness, impact resistance, and flexibility are all crucial properties for typical protective
Surface hardness, impact resistance, and flexibility are all crucial properties for typical protective
coating films. Figure 9 exhibits the pencil scratch hardness test comparisons of samples respect to
coating films. Figure 9 exhibits the pencil scratch hardness test comparisons of samples respect to
fillers’ types and contents. As expected, owing to the similar resin and curing agent, samples exhibit
fillers’ types and contents. As expected, owing to the similar resin and curing agent, samples exhibit
similar pencil scratch hardness of HB when no filler is incorporated in. It is observed that the pencil
Processes 2019, 7, 316 10 of 19

3.2. Physical Properties, UV and Corrosion Resistances of Coating Films

3.2.1. Physical Properties

Surface hardness, impact resistance, and flexibility are all crucial properties for typical protective
coating films. Figure 9 exhibits the pencil scratch hardness test comparisons of samples respect to
fillers’ types and contents. As expected, owing to the similar resin and curing agent, samples exhibit
Processes 2019,
Processes 2019, 7,
7, xx FOR
FOR PEER
PEER REVIEW
REVIEW 10 of
10 of 19
19
similar pencil scratch hardness of HB when no filler is incorporated in. It is observed that the pencil
scratch
scratchhardness
hardnessof ofsamples
sampleswith
withAl(OH)Al(OH)333 increase
increase to to H
Hwhen
whenthethefiller
fillercontent
contentisis
is30.6%.
30.6%.While,
While,forfor
scratch hardness of samples with Al(OH) increase to H when the filler content 30.6%. While, for
samples
samples incorporated
incorporated with
withBaSO
BaSO ,,the
thepencil
pencil scratch
scratch hardness
hardness increased
increased totoHHatatthe
the maximum
maximum BaSO
BaSO
samples incorporated with BaSO4, the pencil scratch hardness increased to H at the maximum BaSO444
44
loading.
loading. Compared
Compared to to BaSO
BaSO444,,, Al(OH)
Al(OH)333 isis more
is efficient
efficient to
more efficient to increase
increase the
the hardness
hardness of of coating
coating film
film at
at
loading. Compared to BaSO Al(OH) more to increase the hardness of coating film at
higher
higher loadings.
loadings. The
The H-A3
H-A3 sample
sample exhibited
exhibited the
thehighest
highest hardness
hardness of
of2H.
2H.
higher loadings. The H-A3 sample exhibited the highest hardness of 2H.
3H
3H
H-A
H-A H-B
H-B
PE-A
PE-A PE-B
PE-B
(-)
hardness/(-)

2H
2H
scratchhardness/

F
F
Pencilscratch
Pencil

HB
HB

B
B
00 17.3
17.3 30.6
30.6 40.2
40.2
Filler contents/
Filler contents/ (wt%)
(wt%)

Figure
Figure 9.Pencil
Figure9.9. Pencilscratch
Pencil scratchhardness
scratch hardnessof
hardness ofsamples.
of samples.
samples.

Figure
Figure10
Figure 10exhibits
10 exhibitsthe
exhibits the results
the resultsof
results ofthe
of theimpact
the impactresistance
impact resistance for
resistance forsamples
for samples in
samples inrespect
in respectto
respect tofiller
to fillertypes
filler typesand
types and
and
contents.
contents. It
contents. It is
It isobserved
is observed
observed thatthat the
that the addition
the addition of
addition of fillers
of fillerscaused
fillers caused a minor
caused aa minor decrease
minor decrease in the
decrease in impact
in the
the impact resistance
impact resistance
resistanceof the
of
of
coating
the films.
coating This
films. may
This be
may due be to the
due todiscontinuities
the in
discontinuities the film
in the matrix
film
the coating films. This may be due to the discontinuities in the film matrix introduced by inorganic introduced
matrix by
introduced inorganic
by fillers,
inorganic
which
fillers,makes
fillers, whichthe
which filmthe
makes
makes lessfilm
the flexible
film less and therefore
less flexible
flexible and lose adhesion
and therefore
therefore to the panels
lose adhesion
lose adhesion thewhen
to the
to panels
panelsreceiving an impact.
when receiving
when receiving an
an
Al(OH)
impact. 3 shows
Al(OH) a slight
shows influence
a on
slight the impact
influence resistance
on the of
impact
impact. Al(OH)3 shows a slight influence on the impact resistance of coatings. For samples
3 coatings.
resistanceFor samples
of incorporated
coatings. For with
samples
Al(OH) 3 , the decrease
incorporated
incorporated with Al(OH)
with of impact
Al(OH) 33,, the
resistance
the decrease
decrease ofoccurs
of impactatresistance
impact the maximum
resistance occursfiller
occurs at the
at loading
the maximum
maximum (40.2%),fillerwith
filler the
loading
loading
reduction
(40.2%), with
(40.2%), of impact
with the resistance
the reduction
reduction of for about
of impact 1.1
impact resistanceJ (from
resistance for 21.2 J
for about to
about 1.1 20.1 J). As
1.1 JJ (from for
(from 21.2 samples
21.2 JJ to
to 20.1 added
20.1 J).
J). As with
As for BaSO
for samples
samples 4,
the reduction
added
added with BaSO
with of impact
BaSO 44,, the
resistance of
the reduction
reduction starts
of at a resistance
impact
impact filler content
resistance of 17.3%.
starts
starts at aa filler
at filler content
content of of 17.3%.
17.3%.

25
25 H-A
H-A H-B
H-B
PE-A
PE-A PE-B
PE-B

20
20
(J)
resistance/(J)
Impactresistance/

15
15

10
Impact

10

55

00
00 17.3
17.3 30.6
30.6 40.2
40.2
Filler contents/
Filler contents/ (%)
(%)

Figure10.
Figure
Figure 10.Impact
10. Impactresistances
Impact resistancesof
resistances ofsamples.
of samples.
samples.

The coating
The coating flexibility
flexibility was
was tested
tested with
with the
the conical
conical mandrel
mandrel bend
bend device.
device. The
The results
results show
show that
that
samples exhibit
samples exhibit good
good flexibility
flexibility up
up to
to filler
filler content
content of
of 40.2%,
40.2%, and
and there
there is
is no
no sign
sign of
of cracking
cracking when
when
the bending
the bending exceeds
exceeds 33 mm
mm mandrel
mandrel diameter,
diameter, which
which is
is the
the minimum
minimum radius
radius of
of the
the cone
cone used
used in
in this
this
study.
study.
In general,
In general, specular
specular gloss
gloss is
is one
one of
of the
the most
most commonly
commonly used
used parameters
parameters for
for evaluating
evaluating surface
surface
Processes 2019, 7, 316 11 of 19

The coating flexibility was tested with the conical mandrel bend device. The results show that
samples exhibit good flexibility up to filler content of 40.2%, and there is no sign of cracking when the
bending exceeds 3 mm mandrel diameter, which is the minimum radius of the cone used in this study.
In general, specular gloss is one of the most commonly used parameters for evaluating surface
optical quality. Figure 11 presents the result of the evaluation of specular gloss at 60◦ . When no filler is
incorporated, the specular gloss varies from 95.8 (PE-C) to 98.4 (H-C). The increase of filler contents
leads to reduction of the specular gloss. At the maximum load of fillers, the specular glosses decrease
Processes 2019, 7, x FOR PEER REVIEW 11 of 19
by about 14.3% (H-B3) and 21.9% (PE-B3), while they fall further down from 47.8% (H-A3) and 49.5%
(PE-A3) in contrast to H-C and PE-C. At the same filler content, samples containing Al(OH)3 exhibit
(PE-A3) in contrast to H-C and PE-C. At the same filler content, samples containing Al(OH) 3 exhibit
much lower levels of gloss than those with BaSO4 . The specular glosses of H-A and PE-A decrease
much lower levels of gloss than those with BaSO4. The specular glosses of H-A and PE-A decrease
significantly to about 50 at the maximum loadings of Al(OH)3 , while samples H-B and PE-B show
significantly to about 50 at the maximum loadings of Al(OH) 3, while samples H-B and PE-B show
glossy films with a specular gloss of about 80.
glossy films with a specular gloss of about 80.

100
H-A H-B PE-A PE-B

90

80
Specular gloss/ (-)

70

60

50

40
0 17.3 30.6 40.2
Filler contents/ (wt%)

Figure 11.
Figure 11. Specular gloss of samples with different
different fillers
fillersand
andfiller
fillercontents
contentsat
at60◦.
60°.

3.2.2.
3.2.2. UV
UV and
and Corrosion
Corrosion Resistances
Resistances
Ultraviolet
Ultravioletlightlightdegrades
degradesthe thecoatings
coatings byby
imparting
imparting energy intointo
energy the films. The energy
the films. The energyof UVoflight
UV
destroys the crosslink by generating heat or breaking chemical bonds. The
light destroys the crosslink by generating heat or breaking chemical bonds. The heat and breakage heat and breakage of bonds of
will lead to the loss of physical and chemical properties of coating films, bringing
bonds will lead to the loss of physical and chemical properties of coating films, bringing in chalking, in chalking, color
change and gloss
color change and reduction.
gloss reduction.
Figure ◦
Figure 12 presents the
12 presents the gloss
gloss retention
retention atat 60
60° after
after aa UV
UV accelerated
accelerated test test against
against 10001000 hh ofof UV
UV
exposure. PE based samples exhibit better overall UV resistances in contrast to
exposure. PE based samples exhibit better overall UV resistances in contrast to H ones when no filler H ones when no filler is
incorporated in. The gloss retention of hybrid-based samples decreased rapidly
is incorporated in. The gloss retention of hybrid-based samples decreased rapidly to 90% of the initial to 90% of the initial
gloss
glosswithin
within200 200h.h.Polyester-based
Polyester-basedsamplessamples have
have thethe
best UVUV
best resistances,
resistances, the gloss retention
the gloss keepskeeps
retention 90%
of the initial gloss for about 700 h in the test chamber, which is 3.5 times of
90% of the initial gloss for about 700 h in the test chamber, which is 3.5 times of that of H basedthat of H based samples.
Besides, it is observed that with the use of Al(OH)3 , the PE-based films exhibit much higher gloss
samples.
retentions thanitthose
Besides, with BaSO
is observed , as shown
that 4with the useinofFigure
Al(OH) 13.3, Compared
the PE-based with Al(OH)
films 3 , the
exhibit muchgloss retentions
higher gloss
of most samples incorporated with
retentions than those with BaSO4, as shown BaSO deteriorate significantly with the increase
4 in Figure 13. Compared with Al(OH)3, the gloss retentions of filler contents.
Samples PE-A1 and
of most samples PE-B1 keepwith
incorporated 90%BaSO
of the4 deteriorate
initial glosssignificantly
for about 630with h andthe530 h against
increase UV exposure.
of filler contents.
Sample PE-A2 keeps 90% of initial gloss for more than 600 h, which is 1.5
Samples PE-A1 and PE-B1 keep 90% of the initial gloss for about 630 h and 530 h against UV exposure. times of that of PE-B2.
When
Sample increasing
PE-A2 keeps the fillers’
90% of loading
initial to the maximum,
gloss for more than the 600
glossh,retention
which isof 1.5PE-A3
timesdecreases
of that ofquickly,
PE-B2.
which is partially due to the much more significant consumption of resin and
When increasing the fillers’ loading to the maximum, the gloss retention of PE-A3 decreases quickly, curing agents in samples
incorporated with Al(OH)
which is partially due to3 . the
A similar
much trendmorecan be observed
significant in samplesof
consumption based
resinonand
hybrid resinagents
curing systems.in
A salt spray test provides a method by which to evaluate the
samples incorporated with Al(OH)3. A similar trend can be observed in samples based on hybridcorrosion resistance in terms
of losssystems.
resin of adhesion at a scribe mark. The rust creepages for scribed samples can be evaluated by
rating grade between 10 and 1 (Table 6). Figure 14 presents the results of corrosion resistance of
samples with different fillers and filler contents. Samples filled with Al(OH)3 exhibit better overall
Processes 2019, 7, x FOR PEER REVIEW 12 of 19

100 100

90 H-C 90
Processes 2019, 7, 316 H-A1 12 of 19
80 80

Gloss retention/ (%)

H-A2

Gloss retention/ (-)

70 H-A3 70
H-B1
60 60
corrosion resistance especially for H-A samples,
which keeps rating number of grade 9 throughout the
H-B2
50 50 PE-C H-B3
whole tested filler contents, while the rating number of H-B PE-A1 samples decrease to grade 7 when the
40 40
filler contents exceed 30.6 wt.%. The corrosion resistances of samples added with BaSO4 deteriorate
PE-A2
30 30 PE-A3
significantly
20
with the increase of fillers contents, especially
20
at the maximum loadings, except for
PE-B1
H-A samples.
Processes 2019, PE-B2
2019,7,7,xxFOR
Processes10 FORPEER
PEERREVIEW
REVIEW 10 12
12 ofof 19
19 PE-B3
0 0
100 0 100 200 300 400 500 600 700 800 900 1000 100
100 0 100 200 300 400 500 600 700 800 900 1000
100
90 Time/ (h) H-C
H-C 90 Time/ (h)
90 H-A1 90
80 H-A1 80

(%)
80 Figure 12. Gloss retention H-A2
of 80 1000 h of UV accelerate test.
samples after
(-)

retention/(%)
H-A2
retention/(-)

70 H-A3 70
70 H-A3 70
Glossretention/

H-B1

Glossretention/
60 800 H-B1 60
60 H-B2 60
H-A H-B2
H-B PE-A PE-B
50 H-B3 50 PE-C
50 700 H-B3 50 PE-C
40 40 PE-A1
40 40 PE-A1
Gloss

PE-A2

Gloss
30 600 30 PE-A2
30 30 PE-A3
PE-A3
20 20 PE-B1
20 500 20 PE-B1
PE-B2
Time/ (h)

10 10 PE-B2
10 10 PE-B3
400 PE-B3
0 0
00 100 200 300 400 500 600 700 800 900 1000 00 100 200 300 400 500 600 700 800 900 1000
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Time/300
(h) Time/ (h) Time/
Time/(h)
(h)
200
Figure
Figure12.
Figure 12.Gloss
12. Glossretention
retentionof
retention ofsamples
of samplesafter
samples after1000
after 1000hhhof
1000 ofUV
of UVaccelerate
UV acceleratetest.
accelerate test.
test.
100
800
800
0 H-A H-B PE-A PE-B
H-A H-B PE-A PE-B
700 0 17.3 30.6 40.2
700
Filler contents/ (wt%)
600
600
Figure 13. Time consumed of samples at 90% of gloss retention.
500
(h)

500
Time/(h)

A salt spray test provides

400 a method by which to evaluate the corrosion resistance in terms of loss
Time/

400
of adhesion at a scribe mark. The rust creepages for scribed samples can be evaluated by rating grade
300
between 10 and 1 (Table 6).300 Figure 14 presents the results of corrosion resistance of samples with
200
different fillers and filler contents. Samples filled with Al(OH) 3 exhibit better overall corrosion
200
resistance especially for H-A 100samples, which keeps rating number of grade 9 throughout the whole
100
tested filler contents, while the
0
rating number of H-B samples decrease to grade 7 when the filler
0 0 17.3 30.6 40.2
contents exceed 30.6 wt.%. The corrosion 0 resistances
17.3 of samples
30.6 added with BaSO 4 deteriorate
40.2
Filler
Fillercontents/
contents/(wt%)
(wt%)
significantly with the increase of fillers contents, especially at the maximum loadings, except for H-
A samples. Figure
Figure13.
Figure 13.Time
13. Timeconsumed
Time consumedof
consumed ofsamples
of samplesat
samples at90%
at 90%of
90% ofgloss
of glossretention.
gloss retention.
retention.

AAsalt 10
saltspray
spraytest
testprovides
providesaamethod
method by which
H-A by which
H-B
to
toevaluate
evaluatethe
PE-A thecorrosion
PE-B corrosionresistance
resistanceininterms
termsofofloss
loss
of adhesion at a scribe mark. The rust creepages for scribed samples can be evaluated
of adhesion at a scribe mark. The rust creepages for scribed samples can be evaluated by rating grade by rating grade
between
between10 10 and
and 11 (Table
(Table 6).
6).9Figure
Figure 1414 presents
presentsthe
the results
resultsof of corrosion
corrosionresistance
resistance ofof samples
samples withwith
different
different fillers
fillers and
and filler
filler contents.
contents. Samples
Samples filled
filled with
with Al(OH)
Al(OH)33 exhibit
exhibit better
better overall
overall corrosion
corrosion
Rating number/ (-)

resistance
resistanceespecially
especiallyforforH-A
H-A8samples,
samples,which
whichkeeps
keepsrating
ratingnumber
numberof ofgrade
grade99throughout
throughoutthe thewhole
whole
tested
tested filler contents, while the rating number of H-B samples decrease to grade 7 when the
filler contents, while the rating number of H-B samples decrease to grade 7 when the filler
filler
contents
contents exceed
exceed 30.6
30.6 wt.%.
wt.%. 7The
The corrosion
corrosion resistances
resistances of of samples
samples added
added with
with BaSO
BaSO44 deteriorate
deteriorate
significantly
significantlywithwiththe
theincrease
increaseof offillers
fillerscontents,
contents,especially
especiallyat atthe
themaximum
maximumloadings,
loadings,except
exceptforforH- H-
AAsamples.
samples. 6
10
10 H-A
H-A H-B
H-B PE-A
PE-A PE-B
PE-B
5
0 17.3 30.6 40.2
99 Filler contents/ (wt%)

Figure 14.
14. Rating
Rating number
number of
of failures
failures at
at scribe
scribe of
of samples
samples after
after 1000
1000 hh of
of salt
salt spray
spray test.
test.
(-)

Figure
number/(-)

88
Ratingnumber/

77
Rating

66

55
Processes 2019, 7, 316 13 of 19

4. Discussion
This study comparatively investigated the effect of Al(OH)3 and BaSO4 on performances of
ultrafine powder coatings. The results show that the incorporation of Al(OH)3 or BaSO4 make little
difference to several properties of the powder paints and finished films, such as AORs of powders, the
flexibility and impact resistance of coating films, while the other properties are influenced significantly
by the fillers’ types and contents. It is shown that the BERs of powders filled with Al(OH)3 is
much higher than those of BaSO4 . The specular gloss of coatings incorporated with BaSO4 is much
higher in contrast to those with Al(OH)3 . Coatings with Al(OH)3 exhibit outstanding corrosion
resistance performances when exposed to salt fog, especially for hybrid-based coatings even at higher
filler content.

4.1. The Effect of Fillers’ Physical Properties on Performances of Powder Paints and Coating Films
The relatively smaller median particle size, higher specific gravity of BaSO4 and higher oil
absorption of Al(OH)3 may partially result in the difference of BER and specular gloss between coating
films filled with Al(OH)3 and BaSO4 respectively.
Samples incorporated with Al(OH)3 exhibit higher BERs in contrast to those containing BaSO4 at
0.93 cm/s of air velocity, as shown in Figure 7. As described earlier, BaSO4 has a much higher specific
gravity than Al(OH)3 . Generally, the higher the specific gravity of particles in the fluidized bed, the
lower bed expansion is achieved at the same air velocity.
The specular glosses of finished films decreased significantly with the addition of Al(OH)3 in
contrast to those of BaSO4 , indicating a stronger matting effect from Al(OH)3 . A matte surface can
scatter the light in all directions and hence the surface appears less glossy. A micro-roughness surface
is necessary for creating the diffuse light scattering responsible for the visual effects of reduced gloss.
Compared with BaSO4 , the better matting effect of Al(OH)3 incorporated coatings are partially due
to the higher oil absorption of Al(OH)3 particles (28g oil/100 g), which is almost 3 times of that of
BaSO4 (10g oil/100 g). During the curing reaction, the non-uniform shrinkage in micro scale which
results from the cross-linking of binder materials, together with the presence of many filler particles
occurs. In general, the higher the oil absorption value of the filler, the more binder it requires to
bind it. Compared with BaSO4 , the naturally higher oil absorption of Al(OH)3 particles lead to the
increase of the content of Al(OH)3 particles in the top-surface of the films and thus the formation of a
micro-rough surface during the curing process. The micro-roughness produced is identified by SEM
images and profile of surface roughness. Figure 15 shows the cross-section view of coating films PE-A3
and PE-B3. The polymer matrix appears darker than the aluminum substrate, as indicated by the
white line which marks out the interface of substrate and the coating film. The coating film adheres
tightly to the substrate, without obvious defects or pores at the interface. The thickness of the coating
film is approximately 38 µm. Figure 16 exhibits the surface roughness of coating films PE-A3 and
PE-B3. The average roughness Ra is the arithmetic average value of the surface profile throughout the
length of the testing surface. The Ra of PE-A3 is more than 1.5 times of that of PE-B3, which is due to
the micro non-uniformity produced during the curing process.
In general, powder coatings are matted by the help of matting agents. They are incompatible with
the coating and can produce micro-roughness of the surface scattering the incident light in different
directions. Generally, matting agents are either polyolefinic waxes or inorganic fillers that can decrease
the gloss level to about 40% of the initial ones when used in concentrations about 4%. However
excessive use of wax can produce haze, yellowing or oily appearance [11,12]. The addition of Al(OH)3
can enhance the matting effect without the incorporation of any other matting agents. The specular
gloss is achieved to blow 50 with the sample (PE-A3) at the maximum loading of Al(OH)3 . In this
case, Al(OH)3 is a good alternative to achieve lower gloss finishes in one shot without the necessity of
adding matting agents.
Processes 2019, 7, x FOR PEER REVIEW 14 of 19
Processes 2019, 7, 316 14 of 19
Processes 2019, 7, x FOR PEER REVIEW 14 of 19

38.46μm
37.88μm
38.46μm
37.88μm

(a) PE-A3-cross-section view (b) PE-B3-cross-section view

(a) PE-A3-cross-section view (b) PE-B3-cross-section view
Figure 15. SEM micrographs of coating films with the addition of Al(OH)3 and BaSO4 respectively.
Figure
Figure 15. SEM micrographs
15. SEM micrographs ofof coating
coating films
films with
with the
the addition
addition of
of Al(OH)
Al(OH)33 and
and BaSO respectively.
BaSO44 respectively.
0.6 0.6
Ra=0.063 μm Ra=0.040 μm
0.6 (μm) (μm) 0.6
(μm) (μm)

0.4 0.4
Ra=0.063 μm Ra=0.040 μm
roughness/
roughness/

0.4 0.4
0.2 0.2
roughness/
roughness/

0.2 0.2
0.0 0.0
of surface

of surface

0.0 0.0
of surface

of surface

-0.2 -0.2
Profile

Profile

-0.2 -0.2
-0.4 -0.4
(a) PE-A3 (b) PE-B3
Profile

Profile

-0.4 -0.4
-0.6 (a) PE-A3 -0.6
(b) PE-B3
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6
-0.6 Length of the surface/ (mm) -0.6 Length of the surface/ (mm)
0.0 0.4 0.8 1.2 1.6 0.0 0.4 0.8 1.2 1.6
Length of the surface/ (mm)
Figure 16. Roughness of the surface of coating films with the addition of Length
Al(OH) of the surface/
and BaSO(mm)
respectively.
Figure 16. Roughness of the surface of coating films with the addition 3of Al(OH)43 and BaSO4
respectively.
4.2. The Effect
Figure 16.of Roughness
Fillers’ Chemical
of theProperties
surface ofoncoating
Performances of Coating
films with Films of Al(OH) 3 and BaSO4
the addition
respectively.
4.2. TheTheEffect
chemical properties
of Fillers’ Chemicalof fillers makeonfor
Properties a great influence
Performances of Coating on the properties of coating films, due
Films
to the
4.2. The interaction between polymer and fillers during the curing processes. The differential scanning
TheEffect of Fillers’
chemical Chemical
properties of Properties
fillers make on Performances
for a great influence of Coating onFilms
the properties of coating films,
calorimetry (DSC) analysis can reveal the effect of chemical properties on the coatings.
due to Thethe interaction
chemical between fillers
properties polymer andforfillers during the curing processes. of The differential
Figure 17 shows the DSC of analysis of make
coatings a H-C,
great influence
H-B3 and H-A3.on theTwo properties
importantcoating events of films,
the
scanning
due to thecalorimetry
interaction (DSC)
betweenanalysis
polymercan reveal
and the
fillerseffect of
during chemical
the curingproperties
processes. on the
The coatings.
differential
curing processes of coatings, the glass transition and the crosslinking are identified. At first, the glass
Figure
scanning 17 shows the
calorimetry DSC
(DSC) analysis
analysis canof reveal
coatings the H-C,
effectH-B3 and H-A3. Two important events of the
transition curves developed much slower at early stages ofofcuring
chemical processproperties
when the on the coatings.
molecular chains
curing processes
Figure of
17 shows coatings, the
thetransition glass
DSC analysis transition
of coatings and the
H-C,stagescrosslinking
H-B3 and are identified.
H-A3. Twowith important At first, the of
events glass
the
formed. Then the glass accelerated at later in accordance the chain network
transition
curing curves
processes developed
of coatings, much
the slower
glass at early
transition stages
and the of curing
crosslinking processare when
identified.the molecular
At◦ first, thechains
glass
formed [41]. With the incorporation of BaSO4 and Al(OH)3 , the Tg increases from 62.1 C (H-C) to 63.9
formed.
◦transition Then thedeveloped
curves glass transition
much accelerated at later stages in accordance withthe the chain network
C (H-B3) and 64.6 ◦ C (H-A3). Thisslower at early
is partially duestages
to the of curing
interaction process
of the when
polymer molecular
resin systems chains
and
formed
formed. [41]. With
Thenfillers, the
the glass incorporation
transition of BaSO and Al(OH) , the T increases from 62.1 °C (H-C) to
hinder accelerated at mobility
later stages in accordance
the curingwith the chain
[42]. network
4 3 g
the inorganic which the molecular during processes Besides,
63.9
formed°C (H-B3) and
[41].ofWith 64.6 °C (H-A3).
the incorporation This is partially
of BaSO(∆H due to the
4 and Al(OH))3,during interaction
the Tg the of
increasesthe polymer
fromgreatly resin systems
62.1 °Cdecreased
(H-C) to
the amount the crosslinking heat released crosslinking scan were
and the(H-B3)
inorganic fillers, which hinder the molecular mobility duringofthe curing processes [42].
by the addition of two fillers in this study. During the curing process, the fillers absorbed systems
63.9 °C and 64.6 °C (H-A3). This is partially due to the interaction the polymer resin parts of
Besides,
andenergy the
the inorganicamount of
fillers,the crosslinking
which hinder heat
the in released
molecular (ΔH ) during the scan were greatly
the resinmobility
systems, during thealso
curing processes [42].
crosslinking
the depending on the filler quantity which is confirmed by other
decreased
Besides, by amount
the the additionof of two
the fillers in this
crosslinking heat study.
released During(ΔH the curing ) process,
during the the
scanfillers
wereabsorbed
greatly
investigations [42–44]. The dispersion of inorganic fillers in the resin systems hinders the mass and
crosslinking
parts of theby
decreased energy depending
the addition on fillers
the filler quantity in the resin thesystems, which isthe also confirmed by
heat transfer, decreasing theofreactivity
two of in
thethis study.
system as During
evidenced curing
by process,
the reduction fillers
in the absorbed
∆Hcrosslinking
other
parts investigations [42–44]. The dispersion of inorganic fillers in the resin systems hinders the mass
of theof the energy processes,
crosslinking dependingasonshown the filler quantity
in Figure 17.in thefillers’
The resin systems,
addition which is also decreased
significantly confirmedthe by
and
other heat transfer, decreasing
investigations [42–44]. Thethe reactivityofofinorganic
dispersion the system fillers asinevidenced
the resin by the reduction
systems hinders the inmass
the
amount of heat released. The ∆Hcrosslinking of H-A3 and H-B3 are about 39% and 37% of the heat
ΔH
andcrosslinking of the crosslinking
heatbytransfer, decreasing processes, as shown in Figureas17. The fillers’ by addition significantly
released sample H-C, which the reactivity
are much lowerofthan the the system
polymerevidenced content of 59.8% theinreduction
H-A3 andin the
H-B3.
decreased
ΔH crosslinking the
of amount
the of heat
crosslinking released.
processes, The as ΔH
shown in
crosslinking of H-A3
Figure and
17. TheH-B3 are
fillers’ about
addition 39% and 37% of
significantly
Meanwhile, fillers with polar groups such as hydrogen bond can interact with the polymeric network,
the heat released
decreased by sample
the amount of heat H-C, whichThe
released. are much lowerofthan
ΔHcrosslinking H-A3 theandpolymer
H-B3 are content
aboutof39% 59.8%and in37%
H-A3 of
thus influencing the chain formation and flexibility during the curing process, consequently increasing
and H-B3. Meanwhile, fillers with polar groups such as
the heat released by sample H-C, which are much lower than the polymer content of 59.8% in H-A3 hydrogen bond can interact with the
and H-B3. Meanwhile, fillers with polar groups such as hydrogen bond can interact with the
Processes 2019, 7, x FOR PEER REVIEW 15 of 19
Processes 2019, 7, 316 15 of 19

polymeric network, thus influencing the chain formation and flexibility during the curing process,
consequently increasing
Tg , decreasing the ∆Hthe Tg, decreasing the ΔHcrosslinking. The H-A3 coatings filled with Al(OH)3
the crosslinking . The H-A3 coatings filled with Al(OH)3 exhibit higher T g and
exhibit higher T g and lower ΔHcrosslinking than those of H-B3, which is partially due to the -OH bond
lower ∆Hcrosslinking than those of H-B3, which is partially due to the -OH bond interacting with the
interacting
polymer with the polymer chain.
chain.

H-C H-B3 H-A3

Tgg=62.1℃
Tgg=63.9℃
Tgg=64.6℃
Hcrosslinking
crosslinking
=18.22 J/g

Hcrosslinking
crosslinking
=7.12 J/g Hcrosslinking
crosslinking=6.72 J/g

30 60 90 120 150 180 210 30 60 90 120 150 180 210 30 60 90 120 150 180 210

Temperature/ (℃)
Figure 17.
Figure 17. DSC
DSC thermograms
thermograms of
of hybrid-based coatings with
hybrid-based coatings with and
and without
without the
the addition
addition of
of fillers.
fillers.

The glass
glass transition
transitiontemperature
temperature(T(T g )g)isisa a
useful
usefulparameter
parameter to to
describe curing
describe propagation
curing propagation andand
can
be
canlinked to mechanical
be linked properties
to mechanical [45]. During
properties the curing
[45]. During the processes, the molecular
curing processes, network network
the molecular mobility
decreases accordingaccording
mobility decreases with the increase Tg [44].of
with theofincrease This can partially
Tg [44]. This canexplain theexplain
partially significantly improved
the significantly
pencil
improvedscratch hardness
pencil scratchofhardness
H-A3 and of H-B3.
H-A3 and H-B3.
Besides, the corrosion resistance is also greatly influenced by the chemical properties of fillers
added. It It is a crucial property for the coating’s application, which strongly depends on a variety of
parameters such such asasquality
qualityofofresin
resinsystems,
systems, chemical
chemical properties
properties of of bulk
bulk materials
materials andand conditions
conditions the
the
filmsfilms exposed
exposed to. to.
TheThe reason
reason thatthat leads
leads to tothethesuperior
superiorcorrosion
corrosionresistances
resistancesof of H-A
H-A could be
interpreted as follows. Firstly, the existence of epoxy in hybrid components, a well-known corrosion
resistance resin, helps maintaining
maintaining a good anti-corrosion
anti-corrosion property. Secondly, a large amount of OH
bonds are exposed to the the surface
surface ofof the
the Al(OH)
Al(OH)33 particles which can interact with the resin chains
through
through hydrogen
hydrogenbond bond[46], as as
[46], shown
shown in Scheme
in Scheme 1. As1.a result, higherhigher
As a result, corrosion resistances
corrosion of samples
resistances of
H-A1,
samples H-A2,
H-A1, H-A3
H-A2,andH-A3
PE-A1 andare obtained
PE-A1 in contrast
are obtained in to those added
contrast to thosewith BaSO
added 4 . With
with BaSO the increase
4. With the
of filler contents,
increase the deterioration
of filler contents, of corrosion
the deterioration of resistance
corrosion is mainly due
resistance to the significantly
is mainly inadequate
due to the significantly
of resin andof
inadequate curing
resin agent, whichagent,
and curing are essential
which are in crosslink
essential inside coatings
in crosslink [47,48].
inside coatings [47,48].

R O
CH2 CH CH 2 O C
O
H
O
Al(OH)3 O H O
O R O CH 2 CH CH2 O C
H
O
R O CH2 CH CH2 O C
Scheme
Scheme 1. Hydrogen bonding
1. Hydrogen bonding between
between hybrid
hybrid resin
resin and
and Al(OH)
Al(OH)33..
Processes 2019, 7, 316 16 of 19

5. Conclusions
Al(OH)3 , a widely used filler in solvent-based coatings and BaSO4 , a popular filler in both
solvent-based coatings and powder coatings, are involved in polyester-epoxy and polyester based
ultrafine powder coatings to make comparative investigations.

1. Several performances of the products are significantly influenced by the type of fillers, such
as BERs and specific gravity of powder paints and specular gloss, pencil scratch hardness and
corrosion resistance of coating films. Powder paints with Al(OH)3 exhibit higher BERs at high
superficial gas velocity than those with BaSO4 , ensuring a uniform gas-solid contact during the
electrostatic spraying process. A significant promotion in matting effect is shown in samples with
Al(OH)3 . It shows great enhancement in pencil scratch hardness of samples added with Al(OH)3
in contrast to those with BaSO4 . PE based samples incorporated with Al(OH)3 show excellent
UV resistances. Hybrid based samples with Al(OH)3 demonstrate outstanding performance of
corrosion resistance.
2. Other properties of powder paints and coating films are slightly influenced by the difference of
fillers’ type, such as the AORs, the flexibility and the impact resistance. Compared to the filler’s
type, the resin system has greater influence on AORs of powder paints. With the addition of
fluidization additives, the AORs of most hybrid-based samples stay within an acceptable range
(<42◦ ), and the powders can be expected to have good flowability during the application process.
Flexibility of films remain stable for sample panels with both fillers. Impact resistance of samples
incorporated with Al(OH)3 is slightly superior than those with BaSO4 .
3. The different performances of coating films with the two fillers are attributed to the difference of
their physical and chemical properties. The more significant matting effect of Al(OH)3 compared
to BaSO4 , is mainly due to the relatively higher oil absorption and micro-rough surface produced
accordingly. The excellent corrosion resistances of hybrid-based samples incorporated with
Al(OH)3 are partially due to that the hydrogen bond of Al(OH)3 strengthens the crosslink of
coating films. The DSC analysis reveals relatively higher Tg and slightly lower ∆Hcrosslinking of
H-A3 samples, which are partially due to the strong interaction between the hydrogen bond and
the polymer chain.

This experimental study provides valuable information for the application of Al(OH)3 to ultrafine
powder coatings. Compared to BaSO4 , the use of Al(OH)3 is expected to bring about a better mechanical
property and durability of the coating film.

Author Contributions: Conceptualization, J.Z. and H.Z.; Methodology, D.C.F.; Software, M.S.Y.; Validation, H.Z.,
H.Z. and W.L.; Formal analysis, W.L.; Investigation, W.L. and D.C.F.; Resources, H.Z. and Y.S.; Data curation, W.L.;
Writing—original draft preparation, W.L. and X.Z.; Writing—review and editing, H.Z. and H.Z.; Visualization,
W.L.; Supervision, H.Z.; Project administration, J.Z.; Funding acquisition, H.Z.
Funding: This research was funded by the Natural Sciences and Engineering Research Council of Canada (NSERC),
Discovery Grant RGPIN-2018-06256.
Conflicts of Interest: The authors declare no conflicts of interest.

Notations
D50 Median particle diameter (50 vol.% of the powder smaller than the diameter) (µm)
AOR Angle of repose, which is defined as the slope measured from the horizontal to the side of a
cone that is formed when the powder is allowed to free fall onto a plate. It is the maximum
angle at which powders can pile up (◦ )
BER Bed expansion ratio, which is the ratio of the bed height at operating conditions to the finally
settled bed height
Glosst=0 Initial gloss at 60◦ (-)
Glosst=x Gloss value at a general time “x” at 60◦ (-)
Processes 2019, 7, 316 17 of 19

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