Progress in Organic Coatings xxx (xxxx) xxxx

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Progress in Organic Coatings

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

Preparation of waterborne epoxy dispersion and its application in 2K

waterborne epoxy coatings
⁎ ⁎
Dan Aia, Ruibin Moa, Huihui Wanga, Yingbiao Laib, Xiang Jianga, , Xinya Zhanga,
a
School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou
510640, China
b
Guangzhou Carpoly New Materials Co. Ltd, Guangzhou 511430, China

A R T I C LE I N FO A B S T R A C T

Keywords: Waterborne epoxy dispersions have excellent permeability and adhesion to various polar substrates and they are
Epoxy resin widely used as coatings and adhesives in industrial applications. Herein we present experimental schemes of a
Emulsifier reactive emulsifier and three waterborne epoxy dispersions prepared for waterborne epoxy coatings. First, the
Waterborne epoxy coatings epoxy groups in polyethylene glycol diglycidyl ether (PEGDGE) and epoxy resin E20 are ring-opened with amino
Epoxy dispersion
hydrogen in ethanolamine, followed by neutralizing with glacial acetic acid (HAc) to obtain an emulsifier for
emulsifying epoxy resins. Then two bisphenol A epoxy resins E20, E51 and a novolac epoxy resin NPPN631 are
employed as emulsified oil phase to prepare waterborne epoxy dispersions with the above emulsifier. And finally
the as-prepared waterborne epoxy dispersions are applied in 2K waterborne epoxy coatings. The results indicate
that when the molar ratio of PEGDGE with an epoxy equivalent of 109 g▪mol−1 and epoxy resin E20 is 2:1, the
synthesized emulsifier possesses the optimal emulsifying ability for epoxy resin, with the Krafft point of 56°C,
and the HLB of 16. The coating films from 2K waterborne epoxy coatings occupy excellent wear resistance,
thermal stability, hardness and mechanical properties. By exploring the curing mechanism, the superior per-
formances of the coatings film prepared by waterborne epoxy dispersion and waterborne epoxy curing agent are
presented.

1. Introduction The chemical modification method is to attach hydrophilic groups

to the structure of the epoxy resin so that it can be emulsified in water
Waterborne coatings are low toxic and tasteless, and less or almost [18]. Pradhan [19,20] used acrylic acid and modified epoxidized soy-
no harm to human health and the environment. Thus they are the future bean oil to synthesize waterborne epoxy acrylate with excellent me-
developing trends of coatings [1–3]. Waterborne epoxy coatings are chanical and thermal properties. Tahami[21] fabricated epoxy-amine
widely used in anticorrosion [4–8], flame retardant [9,10] and other adduct through the reaction between diglycidyl ether of bisphenol A
fields [11–13] due to their good adhesion and chemical resistance. At (DGEBA) and 1,1-iminodi-2-propanol, followed by neutralizing the
present, there are two principle methods for preparing waterborne amine functional group with acetic acid. Pan[22] synthesized epoxy-
epoxy dispersions: phase inversion and chemical modification. acrylic composite latex by emulsion polymerization and compared the
The phase inversion method is to convert the W/O (water droplets mixture of acrylic resin and epoxy resin with composite copolymer.
dispersed in an oil continuous phase, water-in-oil) system into O/W(oil Zhou [23] introduced the carboxyl and hydroxyl group into the main
droplets dispersed in water, oil-in-water) system under high-speed chain of epoxy resin through the reaction of epoxy resin with toluene
shear force [14,15]. Yang [16] studied the phase-inversion emulsifi- diisocyanate and 2,2-dimethylol propionic acid, then neutralized with
cation technique and discovered the emulsification temperature and n, n-dimethylethanolamine to gain water solubility. Zhang[24] mod-
emulsifier concentration played great roles in controlling morphology ified epoxy resin with p-aminobenzoic acid to obtain amphiphilic ma-
and particle size of emulsion. Xu[17] synthesized the emulsion via terials (p-ABA-EP) and investigated the factors influencing the particle
emulsifying epoxy resin by Pluronic block copolymer, and observed the size of emulsion. Mu [25] used graft polymerization to prepare stable
changes of electrical conductivity and viscoelasticity of the system epoxy resin emulsion by vinyl acetate and polyvinyl alcohol (PVA) as
during the phase inversion process. emulsification stabilizer and examined the effects of temperature,

⁎
Corresponding authors.
E-mail addresses: [email protected] (X. Jiang), [email protected] (X. Zhang).

https://doi.org/10.1016/j.porgcoat.2019.105258
Received 17 January 2019; Received in revised form 27 June 2019; Accepted 30 July 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Dan Ai, et al., Progress in Organic Coatings, https://doi.org/10.1016/j.porgcoat.2019.105258
D. Ai, et al. Progress in Organic Coatings xxx (xxxx) xxxx

dosages of initiator, acrylamide, acrylic acid and other functional opening crosslinking reaction of epoxy groups by tertiary amines. Fi-
monomers on the properties of emulsion. nally, the solvents were removed by vacuum distillation and faint
It is not difficult to prepare stable and small-sized waterborne epoxy yellow transparent epoxy emulsifier was obtained.
dispersions by chemical modification. However, most chemical mod-
ification methods are either based on modifying higher molecular 2.3. Preparation of waterborne epoxy dispersion
weight epoxy resins or destroying epoxy groups in epoxy resins, which
may cause insufficient crosslinked density of cured product, conse- 50 g self-made emulsifier and 100 g E51 were added to a vessel. The
quently affecting the performances of waterborne coatings film. temperature of system was maintained 60–70 °C with water bath. Under
Suitable chemical modification to ensure the stability of the dispersion high-speed shearing of 3000 to 4000 rpm, water was slowly added to
and excellent performances of coatings film is still a challenge. The the vessel at a rate of 4 ml/min. The viscosity of the system first
waterborne epoxy dispersion obtained by phase inversion method re- dropped and then slowly rose. When the viscosity peak was reached,
tains the epoxy group in the molecule chain, provides sufficient curing the water dropping speed was increased to 5 ml/min. As more water
reaction sites, and meanwhile achieves higher solid content. In addi- was feeding, the viscosity of the system begun to decline again. When
tion, the technology of phase inversion is more facile, thus it is widely the viscosity suddenly plunged, it indicated that the system completed
applied to actual industrial production. the inversion process from W/O to O/W. At this moment, water was
The disadvantages of the phase inversion are that the particle size of quickly added to adjust the desired solid content of waterborne epoxy
the dispersion is difficult to control, and wide particle size distribution dispersion to 55%. Similarly, the emulsification of NPPN631 and E20
leads to poor stability of dispersion. The key to resolve the defects of the were conducted as the same process.
phase inversion method is to synthesize an emulsifier with good
emulsifying ability for epoxy resins. In this paper, a cationic waterborne 2.4. Preparation of waterborne epoxy coatings
epoxy emulsifier with epoxy resin segment as hydrophobic end and
polyether segment as hydrophilic end was fabricated. The hydrophilic The waterborne epoxy dispersions WEP631, WEP51, WEP20 and
and lipophilic balance (HLB) and emulsifying ability of the emulsifier waterborne epoxy curing agent (Banco901) were mixed at a molar ratio
could be tuned by changing the ratio of epoxy segment to polyether of epoxy group to ammonia hydrogen of 1:1(converted into mass ratio
segment. The emulsifying capacity of the emulsifier was marked of 1.7:1, 1.9:1, 4:1, respectively), then 10% water was added to adjust
through the mechanical stability and particle size of the as-prepared the viscosity. Brushing the waterborne epoxy coatings on tinplate (120
dispersion. Three common and representative epoxy resins E51, E20, mm*50 mm) and glass plate (100 mm*100 mm) with a thickness of
NPPN631 were emulsified with the synthetic emulsifier to prepare 23 ± 3 μm. The films were dried at room temperature for 7 days to
waterborne epoxy dispersions named as WEP51, WEP20, WEP631 re- ensure the dispersions and curing agent reacted completely.
spectively. The coatings films from these dispersions WEP51, WEP20,
WEP631 and waterborne epoxy curing agent both have excellent 2.5. Characterization
properties. By exploring the curing mechanism, the microstructure and
macroscopic properties of the film prepared with waterborne epoxy Fourier transform infrared (FTIR). FTIR spectra of samples were
dispersion and waterborne epoxy curing agent are distinguished from recorded between 4000 cm−1 and 500 cm−1 by a Spectnlm2000 spec-
the film prepared with the epoxy resin emulsified with waterborne trometer (Perkin Elmer Co. USA). The samples were prepared by usual
epoxy curing agent directly. KBr pellet method.
Dynamic light scattering (DLS). The particle size and dis-
2. Experimental persibility of waterborne epoxy dispersion were determined by DLS
(Malvern mastersizer 2000). When measuring the particle size of the
2.1. Materials dispersion, the sample was diluted of 0.2% solid content with deionized
water and sonicated for 10 min.
Bisphenol A epoxy resins (E20, E44, E51, with epoxy equivalent Scanning electron microscope (SEM). SEM was used to observe
weight of 500 g▪mol−1, 227 g▪mol−1, 196 g▪mol−1) were purchased the surface morphology of the coating film. The sample was adhered to
from Shell (America). Phenolic epoxy resin (NPPN631, epoxy equiva- the sample stage with conductive adhesive, and then gold was sprayed.
lent weight of 173 g▪mol−1) was provided by Nanya (China). Thermogravimetric analysis (TGA). TGA was conducted with a
Polyethylene glycol diglycidyl ethers (PEGDGE, with epoxy equivalent Netzsch TG 209 thermo-analyzer instrument. The coating film was
weight of 109 and 266 g▪mol−1) were supplied by Tianjin Guangfu Fine heated in a temperature range of 30–700 °C under N2 atmosphere at a
Chemical Research Institute (China). Ethanolamine (ETA) was pur- heating rate of 10 °C /min.
chased from Tianjin Beichen Founder Reagent Co., Ltd (China). Glacial Differential scanning calorimeter (DSC). The glass transition
acetic acid (HAc) was offered by Sinopharm Chemical Reagent Co., Ltd temperature of the material could be measured by DSC (NETZACH
(China). N-butanol (NBA) and propylene glycol methyl ether (PM) were DSC204, Germany). Taking 4 to 10 mg of coating film sample into the
purchased from Tianjin Damao Chemical Reagent Co., Ltd (China). The crucible and raised temperature from 0 to 200 °C at a rate of 10 °C/min
waterborne epoxy curing agent Banco901 (with active hydrogen under N2 atmosphere.
equivalent weight of 248 g▪mol−1, solid content was 60%) was sup-
plied by Banghe Chemical Co., Ltd (China). 3. Results and discussion

2.2. Synthesis of epoxy resin emulsifier 3.1. Effect of the structure of emulsifier on emulsifying property

ETA, epoxy resin and PEGDGE underwent ring-opening reaction to The PEGDGE introduced in the synthesis of epoxy resin emulsifier
synthesize emulsifier for emulsifying epoxy resin as shown in (Scheme provides a polyether segment which forms hydrogen bonds with water,
1). The typical process was as follows: 100 g E20, 50 g solvents (30 g PM meanwhile, the ether bond is easy to rotate, and thus reducing the
and 20 g NBA) and 43.6 g PEGDGE were charged in a 500 ml four- brittleness of epoxy resins. The emulsifier has both hydrophilic seg-
necked flask with stirring and heated to 80 °C. Then 9.2 g ETA was ments and lipophilic segments in the molecule. According to the prin-
dropwise added into the flask. The system was maintained at 80 °C for ciple of “similarity compatibility”, the higher the structural similarity
4 h, then cooled to 60 °C and added 9 g HAc to neutralize tertiary between the emulsifier and the epoxy resin is, the stronger the mutual
amine. The purpose of neutralization is to avoid the initiation of ring- adsorption/interaction is, and more stable the resulted dispersion

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D. Ai, et al. Progress in Organic Coatings xxx (xxxx) xxxx

Scheme 1. Synthesis of the emulsifier for emulsifying epoxy resins.

would be. Therefore, the molecule of the epoxy resin is considered to

access into the designed molecular structure of the emulsifier.
The types of PEGDGE and bisphenol A epoxy resin have great in-
fluences on the emulsifying property of synthetic emulsifier. Both
PEGDGE and epoxy resin are bifunctional polymers, and a larger epoxy
equivalent weight means a longer molecular chain, thus the corre-
sponding hydrophilicity and hydrophobicity would be stronger. In this
experiment, emulsifiers synthesized from different epoxy equivalents of
PEGDGE and epoxy resins emulsified epoxy resin E51 to obtain a series
of dispersions. The types of PEGDGE and epoxy resin used in the
synthesis could be determined by testing the mechanical stability of
these as-prepared dispersions.
It can be seen from Table 1 that the emulsifier synthesized by
PEGDGE with an epoxy equivalent of 109 g mol−1 and E20 has the
optimal emulsifying ability for epoxy resin, and other emulsifiers have
poor emulsifying ability due to their too strong hydrophilicity. The
mechanical stability was evaluated by a high-speed dispersion machine
stirring with different rotating speed and duration level. (Marked by
levelⅠ, Ⅱ, Ⅲ, Ⅳ, Ⅴ)
Besides the types of PEGDGE and epoxy resins, the ratio of PEGDGE Fig. 1. The particle size distributions of dispersions obtained from emulsifiers
and epoxy resin also affects the hydrophilic-lipophilic ability of the b, c and d.
emulsifier. The more the amount of PEGDGE is charged, the stronger
the hydrophilicity of the emulsifier is. Adjusting the feeding ratio of narrowest size distribution than that of the dispersions obtained from
PEGDGE and E20 to 1:2, 1:1, 2:1, 3:1, and the obtained emulsifiers are emulsifiers b and d with the same amounts. Therefore, the ratio of
respectively recorded as emulsifiers a, b, c, d. Among them, the emul- PEGDGE/E20 is determined to be 2:1. The emulsifier used in the sub-
sifier a is too hydrophobic to be dispersed in water, and is not suitable sequent emulsification and the related tests are all directed to the
used as an O/W emulsifier. The emulsifiers b, c, d all have better emulsifier c.
emulsifying ability, and all the prepared dispersions have mechanical Krafft point is an important characteristic parameter of ionic
stability of gradeⅠ. Meanwhile, the optimum ratio of PEGDGE/E20 emulsifier. If the temperature is below the Krafft point, the surfactant
could be intended by comparing the particle sizes of the dispersions. could not form micelle, therefore the solubility and emulsifying ability
The particle sizes of the dispersions prepared by emulsifying epoxy are very low. With the temperature increases, the solubility increases
resin E51 with emulsifiers b, c, d are shown in Fig. 1, in which the slowly until the temperature rises to the Krafft point, the solubility
dispersion obtained by emulsifier c has the smallest particle size and reaches critical micelle concentration (CMC) and shows a sharp rise.
The emulsifier c was diluted with water to different concentrations of
0.3%, 0.6%, 0.8%, 1.2%, 2%, and slowly increased temperature until
Table 1 the aqueous solution of the emulsifier changed from turbidity to clar-
Mechanical stability of dispersions.
ification. Recording the change in temperature to obtain the curve in
Epoxy equivalent of PEGDGE E20 E44 E51 Fig. 2. It can be seen that the Krafft point of emulsifier c is 56 °C.
The HLB is another important parameter of emulsifier in addition to
109 g mol−1 Ⅰ Ⅱ Ⅳ
266 g mol−1 Ⅲ Ⅳ Ⅴ
Krafft point. The HLB value reflects the hydrophilicity of the surfactant.
The larger the HLB value is, the stronger the hydrophilic ability obtains
Ⅰ) Turned at 3500 r/min for 30 min without delamination. [26]. A convenient technique for measuring the HLB value is the
Ⅱ) Turned at 2500 r/min for 30 min without delamination. emulsification method. 5% emulsifier is mixed with 15% oil phase,
Ⅲ) Turned at 1500 r/min for 30 min without delamination. which is consisted of turpentine (HLB = 16) and cottonseed oil
Ⅳ) Turned at 1500 r/min for 20 min without delamination. (HLB = 6) at appropriate ratio, then dispersing in 80% water at high
Ⅴ) Turned at 1000 r/min for 20 min without delamination.

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Fig. 2. Solubility-temperature curve of the synthetic emulsifier. Fig. 4. FT-IR spectra of E20 and PEGDGE before(a) and after(b) reaction with
ETA.
speed. The stability of a series of samples are compared after standing
for 12 h, the HLB value of the emulsifier is equal to the HLB value of the The emulsifier contains epoxy group in the molecular structure, and
oil phase of the group with the best stability. As can be seen from Fig. 3, could also react with the curing agent without being released into the
the systems with HLB of 8, 10, 12 and 14 in the oil phase have some system, thereby avoiding the adverse effects on the water resistance and
lamination, but the group with HLB value of 16 is the most stable. solvent resistance of the coatings film due to the hydrophilicity of the
Therefore we infer the HLB value of emulsifier c is near to 16. emulsifier.

3.2. FT-IR analysis 3.3. Effect of the amount of emulsifier on the particle size of the dispersions

Fig. 4 shows the changes of functional groups of E20 and PEGDGE The emulsifier emulsified NPPN631, E51 and E20 respectively to
before and after the reaction with ETA when preparing emulsifier c. The obtain three waterborne epoxy dispersions which were recorded as
characteristic absorption peak appearing at 3400 cm−1 belongs to hy- WEP631, WEP51 and WEP20. The particle sizes of the three dispersions
droxyl group, the weaker absorption peak at 3040 cm−1 could be as- are shown in Fig. 5 with different amounts of emulsifier.
signed to the C–H stretching vibration absorption peak of the epoxy It can been seen from Fig. 5 that the particle size of the dispersions
group, and the strong absorption band at 2920 cm-1 is attributed to gradually decreases as the amount of emulsifier increases. In the
methylmethylene group. The two characteristic absorption peaks at emulsifying process, sufficient emulsifier molecules are required to
1500 cm-1 and 1600 cm−1 represent the C]C vibration absorption adsorb on the surface of the water droplets in time to form an interface
peaks of benzene ring, the absorption band at 1100 cm−1 is the anti- film having a certain tension, so that the water droplets repel each other
symmetric stretching vibration absorption peak of CeOeC, and the and maintain a constant size. With the amount of water increases, the
absorption band at 918 cm−1 stands for the absorption peak of epoxy distance between the water droplets would slowly decrease, and the
group. Comparing a with b in Fig. 4, the area of the epoxy peak in a is attraction would gradually increase. Until the water addition reaches a
significantly larger than that in b, and the area of the hydroxyl peak in a certain critical value, the attraction between the water droplets be-
is smaller than that in b. In the synthesis of emulsifier, the epoxy group comes slightly greater than the repulsive force. At this point the surface
in the system undergoes ring-opening reaction with ammonia hydrogen tension is of the minimum and the continuous phase of the system
to form hydroxyl group, resulting in a decrease of the number of epoxy completely inverses from the epoxy resin to water. Thereby an O/W
group and an increase of the number of hydroxyl group in the system. dispersion with small particle size and narrow distribution is achieved.

Fig. 3. The state with different HLB values after 12h.

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Fig. 5. The particle sizes of dispersions obtained by adding 33%, 50%, 66% emulsifier c.

Conversely, if the added emulsifier is too little, there is not enough impacts the stability of the dispersion and is not conducive to the full
emulsifier molecule adsorbed on the surface of the water droplet to reaction of the dispersion with waterborne epoxy curing agent. By
form a strong interfacial film, resulting in little repulsive force between adding 33% of the emulsifier, dispersions with suitable particle sizes
the water droplets. Under a high-speed shearing force, the small water and narrow distributions, and coatings film with higher hardness of
droplets are easily colliding with each other to form large water dro- 2H–3H are obtained.
plets, and consequently the strength of the interface film is further Table 2 shows the storage stability at 25 °C and 60 °C of the dis-
decreased. As the amount of water continues to increase, the large persions with 33% emulsifier. Their solid content also affects their
water droplets dispersed in the continuous phase of the epoxy resin storage stability. The storage stability is better when the solid content is
coalesce into a continuous phase, and the epoxy resin is wrapped to set about 50˜55%.
form larger-sized random particles. In this case some small water dro-
plets have not yet entered continuous phase and are wrapped in the
dispersed phase of the epoxy resin. Thus the phase inversion is in- 3.4. Performances of waterborne epoxy coatings
complete, and a very unstable W/O/W type dispersion is obtained.
The smaller particle size is advantageous for the coatings film The performances of the coatings film prepared by reacting three as-
properties, but if a smaller particle size is desired, more emulsifier is prepared waterborne epoxy dispersions with waterborne epoxy curing
needed. The ether bonds in the emulsifier have toughening effect, and agent Banco901 are shown in Table 3.
in addition, the content of the epoxy group in the emulsifier is also low. The compatibilities of the as-prepared dispersions with the curing
Thereby the crosslinked density of the waterborne epoxy dispersion agent are very well, and the appearances of the coatings film are
reacted with the curing agent is small, which would cause a decreasing transparent, flat and high gloss. Polar groups such as epoxy group and
hardness of the coatings film when the added emulsifier amount is too hydroxyl group in the dispersions increase the adhesion of the coatings
large. When the amount of the added emulsifier is of 50% even 66%, film to the substrates. The adhesion classifications of the coatings film
the hardness of the film is only H, and when it reduces to 33%, the are tested to 1 or even 0 by the cross-cut test, and no square of the
hardness reaches 2H even 3H. If the amount of emulsifier is further lattice is detached or only small flakes of the coatings are detached from
decreased, the particle size would increase to the micron level, which the intersections of the cuts. The impact resistance of the coatings film
was evaluated. The coatings films prepared by WEP631 and WEP51 can

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Table 2
Storage stability at 25 °C and 60 °C of the dispersions with 33% emulsifier.
Solid Content viscosity(25 °C, mpa.s) Stability at 25 °C Stability at 60 °C

EM631 EM51 EM20

65% 11375 9783 10292 2 months, with gelation 2 days, with gelation
60% 8873 7256 9225 2 months, with gelation 2 days, with gelation
55% 3124 1938 2257 3 months, without gelation or sedimentation 5 days, with sedimentation
50% 2036 1226 1341 3 months, without gelation or sedimentation 6 days, with sedimentation
45% 1573 1015 1136 2 months, with sedimentation 3 days, with sedimentation
40% 1022 896 872 2 months, with sedimentation 3 days, with sedimentation

Table 3
Performances of 2 K waterborne epoxy coatings films.
performances WEP631+Banco901 WEP51+Banco901 WEP20+Banco901 test methods

appearance Smooth, transparent Smooth, transparent Smooth, transparent visual inspection

surface drying time 50min 60min 30min ISO 1517-1995
gloss(60°) 107.4 103.3 96.6 ISO 2813-2014
pencil hardness 3H 2H H ISO 15184-2012
flexibility ≤1mm ≤1mm ≤1mm GB/T 1731-1993
impact resistance 100cm 100cm 50cm ASTM D2794-93
adhesion(level) 1 0 0 ISO 2409-2013
wear resistance (750 g/500 r, g) 0.003 0.011 0.016 ISO 7784-2:2016
acid resistance (10%H2SO4,48 h) blistering pass blistering ISO 2812-2007
alkali resistance (20%NaOH,72 h) pass pass slightly white ISO 2812-2007
water resistance (7 days) pass pass slightly white ASTM D870-2015

Fig. 6. Nanoindentation modulus-displacement curves of the waterborne epoxy

resin coatings film.
Fig. 7. DSC curves of coatings films prepared by reaction of three dispersions
with waterborne curing agent.
withstand 1 kg of steel ball falling from a height of 100 cm without any
cracks, and the film prepared by WEP20 can withstand the impact of
film is only H.
50 cm height. Both the wear resistance of the coatings films are also
Nanoindentation technique was also employed to make the me-
excellent. After being abraded by the 750 g abrasive rubber wheel for
chanical performance more justified. In Fig. 6, the film prepared by
500 r, the masses of the coatings film are only lost by 0.003 g, 0.011 g
WEP631 has the highest modulus of 13.7 GPa and an average modulus
and 0.016 g. The epoxy functionality of the phenolic epoxy resin
of 4.6 GPa within 500 nm displacement, while film of WEP51 has an
NPPN631 is greater than 2, and the epoxy group content in the mole-
average modulus of 4.3 GPa and film of WEP20 has an average modulus
cule is higher than that of the bisphenol A epoxy resin E51 and E20,
of 4.2 GPa, respectively. This is in accordance with the results in Table 3
thus the surface drying time of NPPN631 is relative shorter. In addition,
that waterborne epoxy resin coatings films prepared from 3 different
the higher epoxy content also increases the crosslinked density, which
types of epoxy resin have an overall excellent mechanical performance.
improves the hardness and wear resistance of the film. However,
WEP631 needs to react more curing agent during its curing process,
which leads to the alkalinity of the film becomes stronger, and but poor 3.5. Thermal properties of waterborne epoxy coating
acid resistance of the coatings film is obtained. E20 itself is of solid-state
at room temperature. When the water is evaporated, the coatings film is 3.5.1. Glass transition temperature
already dry, thus the surface drying time of WEP20 is the minimum. The glass transition temperatures (Tg) of the 2 K coatings film pre-
However, due to the low epoxy content of WEP20, the hardness of the pared by WEP631, WEP51, WEP20 are measured by DSC as shown in
(Fig. 7). All the waterborne epoxy coating films have only one Tg, which

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the crosslinked density. The higher epoxy group content in WEP631

provide more curing sites of the reaction with Banco901, and thus the
crosslinked density of the cured product is naturally higher. The Tg of
the coatings film prepared by WEP631 is 16 °C higher than those of
films made by WEP51 and WEP20. It also confirms that the coatings
film formed by WEP631 is more excellent in some mechanical prop-
erties. Although the epoxy value of E20 is lower than that of E51, there
are more rigid benzene ring structure in the molecule, thus the Tg of
WEP20 is not much different with the Tg of WEP51.

3.5.2. Thermogravimetric analysis

Fig. 8 presents the thermogravimetric analysis (TGA) curves of
coatings film, and the thermal decomposition temperatures are shown
in Table 4. The broad weight-loss stages of all coatings film between
300–400 °C are corresponding to the fracture and decomposition of the
network structure of the cured product at high temperature. The
thermal stability of the coatings film prepared by WEP631, WEP51,
WEP20 is gradually reduced. It attributes to the higher the crosslinked
Fig. 8. TG curves of coatings film. density of the cured product, the more energy is required to destroy the
structure.
Table 4
Thermal properties of coating films. 3.6. Comparison of curing mechanisms of two waterborne epoxy coating
systems
Sample Tdec1a (℃) Tdec2b (℃) Tdec3c (℃)

WEP631+Banco901 327 346 387 In the practical application of waterborne epoxy coatings, especially
WEP51+Banco901 312 331 386 in the field of floor paint, some waterborne epoxy curing agents have
WEP20+Banco901 312 331 377 both curing and emulsifying properties and can be used directly with
a solvent-based epoxy resins [27,28]. This semi-solvent and semi-aqu-
Thermal decomposition temperature of 5% weight loss.
b eous system has many drawbacks in comparison with the all-water
Thermal decomposition temperature of 10% weight loss.
c
Thermal decomposition temperature of 50% weight loss. system. In Fig. 9, a and b are the SEM images of the film obtained by
reaction of WEP51 and Banco901, the surface of the film is smooth and
indicates that the dispersion and the curing agent are not simply flat. c and d are the SEM images of the film by directly reaction of E51
blended physically, and a sufficient curing reaction is carried out to and Banco901, but there are many bumps and holes on the surface of
obtain a uniform coatings film. Due to the relative molecular mass of the film. The distinction in surface microstructure of the coatings film
the epoxy resin itself is low, the Tg of the cured film mainly depends on could be explained from the different curing mechanisms of the two
systems.

Fig. 9. SEM of the films obtained by reaction of WEP51 with Banco901 (a, b), and E51 with Banco901 (c, d).

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Fig. 10. The curing schematic of oilborne epoxy resin with waterborne epoxy curing agent.

Fig. 11. The curing schematic of waterborne epoxy dispersion and waterborne epoxy curing agent.

Fig. 12. TG and DTG curves for two types of coatings film.

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D. Ai, et al. Progress in Organic Coatings xxx (xxxx) xxxx

The curing mechanism of semi-solvent and semi-aqueous system is National Natural Science Foundation of China (51576070).
represented in Fig. 10. After the waterborne epoxy resin curing agent
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