Materials Research Express

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Effects of triphenyl phosphate (TPP) and nanosilica on the mechanical

properties, thermal degradation of polymer nanocomposite materials and
coating based on epoxy resin
To cite this article before publication: Huynh Le Huy Cuong et al 2021 Mater. Res. Express in press https://doi.org/10.1088/2053-1591/ac2098

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Page 1 of 15 AUTHOR SUBMITTED MANUSCRIPT - MRX-123762.R1

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3 1 Effects of triphenyl phosphate (TPP) and nanosilica on the mechanical properties, thermal
4

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5 2 degradation of polymer nanocomposite materials and coating based on epoxy resin
6 3
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4 Cuong Huynh Le Huy1*, An Truong Thanh2, Long Huynh Bao3
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1,2,3
9 5 Faculty of Chemical Engineering, Ho Chi Minh City University of Food Industry (HUFI),

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10 6 Ho Chi Minh City, VietNam
11 *
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7 Corresponding author: Email:1*cuonghlh@hufi.edu.vn. Phone number:+84909500601
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13 8 antt@hufi.edu.vn; 3 longhb@hufi.edu.vn
14 9
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10 Abstract

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17 11 Epoxy resin DER 671X75 cured with hardener T31. Epoxy polymer composite materials DER 671X75/T31 were
18 12 improved the mechanical properties, thermal stability by triphenyl phosphate (TPP) and nanosilica (fumed silica
19 13 S5505). Triphenyl phosphate and nanosilica were dispersed in epoxy resin DER 671X75 by mechanical stirring and
20 14 ultrasonic vibration. The structural morphology of materials was characterized by Scanning Electron Microscopy
21 15 (SEM) and Transmission Electron Microscopy (TEM). The thermal stability and thermal properties of materials were
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characterized by Thermo Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). The results
showed that triphenyl phosphate with a content of 5 wt % in epoxy resin DER 671X75 improved the mechanical
properties of epoxy polymer coating film DER 671X75/T31 with an impact strength increased 25 %. The contents of
5 wt % triphenyl phosphate and 1 wt % nanosilica in epoxy resin DER 671X75 improved the impact strength of
epoxy polymer coating film DER 671X75/T31 by 125 %. The thermal stability of epoxy nanocomposite materials
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DER 671X75/5 % triphenyl phosphate/1 % nanosilica/T31 increased 45.35 %. Epoxy coatings based on epoxy resin
29 22 DER 671X75/5 % triphenyl phosphate/1 % nanosilica/pigments/fillers/additives/hardener T31 achieved mechanical
30
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23 properties, physical chemistry properties for coating and, had thermal degradation over 500 oC.
32 24
33 25 Keywords: Triphenyl phosphate, nanocomposite, thermal degradation epoxy coatings, thermal properties, flame
34 26 retardants
35 27
36 28 1. INTRODUCTION
37 29 Epoxy resins have been widely used for coatings, composites, adhesives, and molding materials due to their chemical
38
30 resistance, good adhesion, and anti-corrosion [1]. However, because of many aromatic rings in chemical structure,
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40 31 epoxy resins are often hard and brittle. Flame resistance and thermal stability are other restrictions of epoxy resins
41 32 [1,2,3,4]. To improve the disadvantages of epoxy resins, it can be done by modifying the main structure or replacing
42 33 curing agents, or adding reinforcement additives [1,5]. In recent years, one of the effective methods to increase the
43 34 thermal stability of epoxy resins and polymers has been applied is the addition of flame retardants such as halogen
44 35 compounds, antimony oxide, zinc borate, phosphorus compounds [2-21]. Improving the toughness of epoxy resins
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36 and polymer by nanocomposite structures has also been studied [22-28].
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37 Halogen compounds are highly effective against fire, but often produce toxic products when burned, so their use is
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48 38 limited [6-8]. As a substitute for halogen compounds, phosphorus compounds show excellent heat resistance, exhibit
49 39 high flame resistance, and are completely environmentally friendly [8-21]. Combustion of phosphorus compounds is
50 40 low, has low toxicity, and forms a stable carbonization layer after burning [9-11]. The carbonization layer can
51 41 prevent further pyrolysis of respective polymers, and also inhibits the use of the substance inside the product which
52 42 is thermally decomposed into the gas phase [8]. Inorganic phosphorus flame retardants mainly refer to red
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43 phosphorus [12], ammonium polyphosphate (APP) [13]. Organic phosphorus flame retardants include phosphonates,
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55 44 phosphate esters, organic phosphorus salts, phosphorus heterocyclic compounds, triphenyl phosphate (TPP) [14-20].
56 45 Organic phosphorus flame retardants are one class of flame retardants with outstanding flame retardant properties for
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 AUTHOR SUBMITTED MANUSCRIPT - MRX-123762.R1 Page 2 of 15

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3 1 epoxy resin [19]. The main advantages of organic phosphorus flame retardants are low smoke emission, low toxicity,
4 2 and environmental friendliness [8, 14-21].

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3 In recent times, polymer composite materials with nanoparticles have been increasingly studied and applied [22-26].
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4 Nanocomposite based on epoxy resin Epon 828 with 5-10 wt % nanosilica (Aerosil R974) increased UV resistance
8 5 when formed film [22]. Modification of nanosilica by silane agents such as 3-amino propyl trietoxy silane (KH-550),
9 6 3-glycidoxy propyl trimethoxy silane (KH-560) and 3-metacryloxy propyl trimethoxy silane (KH-570), used in

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10 7 synthesizing of poly (methyl methacrylate MMA-2-hydroxyethyl methacrylate HEMA), increased surface activity
11 8 [23]. Nanocomposite based on Bisphenol-A epoxy resin (Araldite® GY 6010) with 0-3 wt % nanosilica Aerosil
12 9 R200 treated with γ-amino propyl trietoxy silane (Amino A-100) increased mechanical properties and increased the
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10 glass transition temperature (Tg) according to the content of nanosilica [24]. Nanosilica (fumed silica S5505) with a
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15 11 content of 1 wt % increased the mechanical properties of nanocomposite materials based on epoxy resin DER
16 12 671X75 cured with Epicure 3125 [25]. Nanocomposite materials based on epoxy-silicon resin were reinforced with a

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17 13 content of 7 wt % nanoclay that increased the decomposition temperature for 60 wt % loss of clay reinforced Si-
18 14 epoxy composites and improved mechanical properties with a content of 5 wt % clay reinforced Si-epoxy composites
19 15 [26]. Nanocomposites based on phenol novolac epoxy resin were modified by unsaturated polyester resin and then
20 16 reinforced using sasobit and silica nanoparticles at the different filler. Results showed that increasing the content of
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17 wt % silica nanoparticles could improve both thermal and mechanical properties, but increasing the content of more
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than 3 wt % silica nanoparticles could lead to a decrease in the mechanical properties [27]. Generally, the addition of
nanomaterials in composite materials improved the mechanical properties, fracture toughness if the application type,
suitable process, loadings, size, type of nanomaterials were implemented appropriately [28]. In the study [29],
authors report a flame retardant epoxy nanocomposite reinforced with 9,10-dihydro-9-oxa-10-phosphaphenantrene-
10-oxide (DOPO)- tethered SiO2 (DOPO-t-SiO2) hybrid nanoparticles (NPs). The DOPO-t-SiO2 NPs were
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23 successfully synthesized through surface treatment of SiO 2 NPs with (3-glycidyloxypropyl)trimethoxysilane
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30 24 (GPTMS), followed by a click reaction between GPTMS on SiO2 and DOPO. The epoxy nanocomposites with
31 25 DOPO-t-SiO2 NPs as multifunctional additive exhibited not only high flexural strength and fracture toughness but
32 26 also excellent flame retardant properties and thermal stability.
33 27 Most previous studies have shown polymers were reinforced with suitable contents of weight nanoparticles that the
34 28 mechanical properties of polymer composites were improved and flame retardant additives increased the thermal
35 29 stability of polymer composite materials. In addition, there are currently no specific reports on studies using
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30 triphenyl phosphate (TPP) to increase the thermal stability of epoxy resins. Because of these studies, the combination
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38 31 of triphenyl phosphate (TPP) as a flame retardant and nanoparticles nanosilica to form nanocomposite based on
32
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39 epoxy resin has prospected to be more improvement of mechanical properties and thermal stability of polymer
40 33 nanocomposite materials.
41 34 In this work, we focus on studying the effects of triphenyl phosphate (TPP) and nanosilica on the mechanical
42 35 properties and thermal stability of the nanocomposite based on epoxy resin DER 671X75 cured with hardener T31
43 36 and its application in epoxy coating.
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46 38 2. MATERIALS AND METHODS
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47 39 2.1. Materials
48 40 Epoxy resin DER 671X75 (Bisphenol A diglycidyl ether (DGEBA)) with an epoxy equivalent weight (EEW) of 430-
49 41 480 g/eq was purchased from Dow Chemicals. Hardener T31 (phenolic modified amine hardener) as epoxy resin
50 42 curing agent with amine number of 450-550 mgKOH/g was purchased from Zhenjiang Danbao Resin (China).
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43 Nanosilica (S5505-Sigma). Triphenyl Phosphate (TPP) as phosphorus flame retardant (China). Pigments: Oxide Iron
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44 (China), Zinc Phosphate (France), Talc Filler (Taiwan). Crayvallac super (Arkema-France) as a rheology additive of
54 45 high performance is suitable for a wide range of solvent-based, high-solids, and solvent-free applications. The
55 46 plasticizer of Dioctyl Phthalate (DOP) (China). Troysperse CD1 (Thailand) is a general-purpose polymeric pigment
56 47 dispersant and wetting additive for non-aqueous systems. Solvents: Xylene, Toluene, Acetone (China).
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3 1 2.2. Preparation of polymer composite materials and coating film samples
4 2 2.2.1. Method of dispersing triphenyl phosphate into epoxy resin DER 671X75

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3 Triphenyl phosphate with a content of 5 wt % to disperse in epoxy resin DER 671X75. Added 5.00 g of triphenyl
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4 phosphate (TPP) into 100.00 g of epoxy resin DER 671X75. All experimental chemicals were put in a 250 ml glass
8 5 beaker and stirred at 500 rpm for 30 minutes, increased stirring speed to 1000 rpm for 60 minutes, continued to
9 6 increase stirring speed to 2000 rpm for 240 minutes. Investigating of the triphenyl phosphate contents in epoxy resin

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10 7 DER 671X75 was 3 %, 5 %, 7 % by weight.
11 8 2.2.2 Method of dispersing nanosilica into epoxy resin DER 671X75
12 9 Dispersion of nano silica with a content of 1 wt % according to the study [25] that increased of mechanical properties
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10 polymer coating film based on epoxy resin DER 671X75/hardener Epicure 3125. Weigh 1.00 g of nanosilica S5505
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15 11 into a 250 ml glass beaker. Added a certain amount of acetone solvent (5.00 g) to wet and swell nanosilica at a
16 12 stirring speed of 200 rpm for 30 minutes. Then, added 100 g of epoxy resin DER 671X75 and increased the stirring

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17 13 speed to 2000 rpm for 30 minutes, followed by ultrasonic vibration for 50 minutes.
18 14 2.2.3. Method of dispersing nanosilica and triphenyl phosphate into epoxy resin DER 671X75
19 15 First, nanosilica S5505 (amount of 1.00 g) was dispersed into epoxy resin DER 671X75 (amount of 100.00 g)
20 16 according to item 2.2.2 with a content of 1 wt %. Then, dispersed triphenyl phosphate (amount of 5.00 g) into the
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17 mixture of epoxy resin DER 671X75/1 wt % nanosilica according to the method in item 2.2.1.
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2.2.4. Preparation of polymer composite materials samples for analysis
Epoxy polymer composite materials samples were cured with hardener T31. Dried samples at 110 oC for 2 hrs to
cure completely. The samples were thinned about 50 μm for scanning SEM images. Completely cured samples were
used for TG-DSC thermal analysis. The steel samples were prepared according to standards. The surface of samples
was treated by mechanical methods of sanding, rinsing oil with acetone solvent, and dried at 100 oC for 1 hr.
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23 Polymer coating film samples were coated on the treated steel by rolling method with the dry film thickness of 70-90
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24 μm.
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31 25 2.3. Analytical methods of polymer composite materials samples
32 26 Dispersion of triphenyl phosphate and nanosilica into epoxy resin DER 671X75 used the mechanical stirrer IKA-RW
33 27 20 (Germany) and ultrasonic device Sonics Vibram cell model CV334 (USA). The gel contents of polymer
34 28 composite samples were determined by the method of extraction with acetone solvent in the Soxhlet set with a period
35 29 of 10-12 hrs. TEM images were used for the evaluation of nanosilica dispersion in epoxy resin DER 671X75 by
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30 TEM Jeol model JEM 1400, Japan. Dispersion of triphenyl phosphate in epoxy resin DER 671X75 was determined
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38 31 by a scanning SEM image (SEM Jeol model JSM-IT 200, Japan). The thermal stability and thermal properties of
32 polymer composite materials were characterized by TG-DSC on Setaram Labsys Evo (TG-DSC 1600 oC).
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40 33 2.4. Standards for determination of mechanical properties of polymer coating films
41 34 The mechanical properties of polymer coating films are determined according to standards such as ISO, ASTM, and
42 35 JIS. The flexibility of polymer coating films is determined according to standard ISO 1519:2002 (Erichsen, model
43 36 266). Coating films are bent through the shafts of metal cylinders with a diameter of 2 - 20 mm on the measuring
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37 instrument. The flexibility of coating films is expressed as the minimum diameter of the bending shaft which
46 38 polymer coating films have not been damaged. The impact strength of coating films is determined according to
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47 39 standard ISO 6272:2002 (Erichsen, model 304) by using mechanical force to damage coating film. Impact strength
48 40 of coating films is expressed as kG.cm which means that the maximum height (in cm) from which a load of mass 1
49 41 kG falls freely on the specimen plate without causing damage to coating films. Adhesion of coating films is
50 42 determined according to standard ASTM D3359-93 (Erichsen, model 295). Adhesion of coating films is determined
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43 based on the percentage of cells that are peeled off when coating films are cut into 1 mm × 1 mm cells and the
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44 adhesive tape is applied. The pencil hardness of coating films is determined by standard JIS K5400-90. The pencil
54 45 hardness of polymer coating films is the hardness of the pencil in front of the pencil having a hardness that will
55 46 scratch coating films. Dry film thickness is determined according to ASTM D1005 (Erichsen, model 296) or
56 47 Vietnam National Standard TCVN 9406: 2012 (MiniTest 3100), using an electronic dry film thickness gauge with a
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3 1 magnetic induction probe for magnetic metal substrates such as iron and steel. Before measuring dry film thickness,
4 2 the instrument needs to be calibrated on a standard membrane. Gently press and hold the probe until the instrument

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3 displays the measurement result (approximately 2 seconds to 3 seconds).
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8 5 3. RESULTS AND DISCUSSION
9 6 3.1. Effects of triphenyl phosphate on the mechanical properties and thermal stability of epoxy polymer

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10 7 composite material DER 671X75/hardener T31
11 8 3.1.1. Dispersing of triphenyl phosphate into epoxy resin DER 671X75
12 9 The gel content of epoxy polymer composite material DER 671X75/hardener T31 was determined by the method of
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10 extraction with acetone solvent in Soxhlet set a period of 10-12 hrs. The results showed that the curing ratio between
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15 11 epoxy resin DER 671X75 and hardener T31 was 100: 30 (wt/wt) that obtained the highest gel content. Epoxy resin
16 12 DER 671X75 and curing agent T31 achieved an optimal reaction ratio that reached the highest gel content. When the

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17 13 ratio between epoxy resin DER 671X75 and hardener T31 was not suitable, there would exist the non-reactive of
18 14 epoxy resin DER 671X75 or T31 curing agent was residual, would be dissolved in acetone solvent, so the gel content
19 15 was low. Thus, the highest gel content weight epoxy resin/hardener with curing ratio: epoxy resin DER
20 16 671X75/hardener T31 was 100: 30 (wt/wt) that was used for curing epoxy composite material samples. This result
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17 was similar to the study [25] when using hardener Epicure 3125 for curing epoxy resin DER 671X75.
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The content of triphenyl phosphate is 5 wt % in epoxy resin DER 671X75 to investigate the method of dispersion.
The SEM image of epoxy polymer composite material DER 671X75/5 % triphenyl phosphate/T31 is shown in
Figure 1:
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40 Figure 1. SEM image of epoxy polymer composite material DER 671X75/5 % triphenyl phosphate/T31
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21 The SEM image from Figure 1 shows that triphenyl phosphate is well dispersed in epoxy resin DER 671X75. Thus,
43 22 the method of dispersing triphenyl phosphate into epoxy resin DER 671X75 by mechanical stirring is suitable.
44 23 Figure 1 also shows that triphenyl phosphate crystals are evenly dispersed and separated on epoxy resin. So, the
45 24 method of dispersion triphenyl phosphate by mechanical stirring is used to investigate the contents of triphenyl
46 25 phosphate dispersing into epoxy resin DER 671X75.
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47 26 3.1.2 Mechanical properties of epoxy polymer composite film DER 671X75/triphenyl phosphate/hardener T31
48 27 The contents of the investigation are 3, 5, 7 wt % triphenyl phosphate in epoxy resin DER 671X75. The mechanical
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28 properties of epoxy coating films DER 671X75/ triphenyl phosphate/T31 are shown in Table 1.
51 29 The results from Table 1 show that mechanical properties of polymer coating films such as flexibility, pencil
52 30 hardness, adhesion are good to samples and there was almost no significant difference with the contents of 3, 5, 7 wt
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53 31 % triphenyl phosphate. The flexibility of coating film samples is all 2 mm, indicating that epoxy coating films have
54 32 very good flexibility. To determine flexibility, coating films are bent through the shafts of metal cylinders with a
55 33 diameter of 2 - 20 mm on the measuring instrument. The flexibility of coating films is expressed as the minimum
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3 1 diameter of the bending shaft which the polymer coating films have not been damaged (flaking, peeling, tearing,
4 2 scratch, etc). The flexibility of coating films is 2 mm, which means that coating films are bent over a 2 mm diameter

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3 shaft without damaging coating films. The lower the test shaft diameter is, the better flexibility of coating films is.
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4 Table 1. Mechanical properties of epoxy coating films
8 Sample Composition
Dry film Impact strength Flexibility Pencil
Adhesion
9 thickness (µm) (kG.cm) (mm) hardness

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10 E0 Epoxy DER 671X75/T31 76.23 20 2 5H 5B
11 Epoxy DER 671X75/3 %
12 E3TPP 78.9 20 2 4H 5B
triphenyl phosphate/T31
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14 Epoxy DER 671X75/5 %
E5TPP 83.38 25 2 5H 5B
15 triphenyl phosphate/T31
16 Epoxy DER 671X75/7 %

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E7TPP 75.15 22.5 2 3H 5B
17 triphenyl phosphate/T31
18 5 Normally, when coating films are bent across the shaft, coating films often peel off with a low diameter shaft. The
19
6 flexibility of coating films is related to the adhesion of coating films on the test steel substrate. The better adhesion of
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21 7 coating films is, the better flexibility of coating films is. To determine the adhesion of coating films on the steel
22 8 substrate, cut 100 squares of 1 mm x 1 mm with a 1 mm slotted knife on coating films and apply adhesive tape to the
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100 cells. Adhesion of coating films on the steel substrate is determined based on the percentage of cells that are
peeled off the steel substrate when the adhesive tape is removed. Adhesion 5B means that when the adhesive tape is
removed, 0 % of the cells are peeled off from the steel substrate, the adhesion of the coating film is very well. If the
amount of cells peeled off is less than 5 %, the adhesion is 4B (according to ASTM D 3359 – 97). The pencil
hardness of coating films is determined based on the hardness of the pencil tip causing scratches on the coating films.
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29 14 The pencil hardness of coating films is 5H which means using a pencil with a hardness of 5H will not scratch the
30 15 coating film, but a pencil with a hardness of 6H will cause scratches to the coating film. Impact strength of coating
31 16 films is determined by using a load of mass 1 kilogram (kG), raising to a specified height (cm) from low to high,
32 17 falling freely, impacting the coating film and causing damage to the coating film (ASTM ISO 6272:2002, Erichsen,
33 18 model 304). The value of the impact strength is determined at the highest position of the load without causing
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19 damage to the coating film. The impact strength of the coating film is 20 kG.cm which means that the maximum
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36 20 height of 20 cm from which a load of mass 1 kG falls freely on the specimen plate without causing damage to the
37 21 coating film. The impact strength of coatings film depends on the brittleness of coating films. Due to many aromatic
38 22 rings in chemical structure, epoxy resins are brittle [1]. Epoxy resin DER 671X75 has many aromatic rings in
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39 23 chemical structure and hardener T31 as phenolic modified amine hardener in which there are many aromatic rings.
40 24 So, epoxy polymer composite DER 671X75/hardener T31 has more aromatic rings, epoxy coating films are brittle
41 25 and the impact strength of epoxy coating film DER 671X75/T31 is only 20 kG.cm. Adding content of 5 wt %
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26 triphenyl phosphate (sample E5TPP), epoxy coating film DER 671X75/5 % triphenyl phosphate/T31 improve impact
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44 27 strength from 20 kG.cm to 25 kG.cm (increased 25%). Triphenyl phosphate has also acted as a reinforced filler for
45 28 epoxy polymer, epoxy resin is a substrate polymer that binding triphenyl phosphate fillers, the optimum ratio
46 29 between fillers and matrix polymer improve the mechanical properties of polymer composite. The mechanical
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47 30 properties of epoxy coating film DER 671X75/T31 are the best with the E5TPP sample (the content of 5 wt %
48 31 triphenyl phosphate). The content of 3 wt % triphenyl phosphate in epoxy resin DER 671X75, properties of epoxy
49 32 polymer composite DER 671X75/3 % triphenyl phosphate/T31 show the properties of epoxy resin DER 671X75 due
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33 to the low content of weight triphenyl phosphate filler. The content of 7 wt % triphenyl phosphate, the content of
52 34 weight epoxy resin DER 671X75 is not enough to cover and bond triphenyl phosphate filler and thus, properties of
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53 35 epoxy composite DER 671X75/7 % triphenyl phosphate/T31 show the properties of triphenyl phosphate, that the
54 36 reason for low mechanical properties of epoxy coating films.
55 37 3.1.3. Thermal stability of epoxy polymer composite material DER 671X75/triphenyl phosphate/hardener T31
56 38 The TG-DSC thermal analysis diagram of epoxy polymer composite material DER 671X75/hardener T31 is shown
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21 Figure 2. TG-DSC thermal analysis diagram of epoxy polymer composite material DER 671X75/T31
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Sample Temperature (°C)

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The TG-DSC thermal analysis results of epoxy polymer composite material DER 671X75/T31 are presented in Table

Table 2. TG-DSC thermal analysis results of epoxy polymer composite material DER 671X75/T31
TG |rs |s (%)
100
HeatFlow |-bs |s (µV)
0
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29 69.224136 100.0053 -0.404055
30 150.070038 99.47541 0
31 158.0567 99.26522 0.000699
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234.078735 96.27925 0.349739
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34 339.959869 86.88529 1.204957
35 374.107239 61.80695 -0.695244
36 484.610413 17.18802 -0.047534
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500.040772 16.52761 -0.000881
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6 The results from the TG-DSC thermal analysis diagram in Figure 2 and Table 2 show that the starting temperature
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40 7 decomposition of epoxy polymer composite DER 671X75/T31 is about 150-158 oC. In this temperature range, the
41 8 decomposition is mainly due to the evaporation of solvents. The strongest decomposition temperature of the sample
42 9 corresponds to the peak with the largest energy on the DSC curve (HeatFlow 1.204957 µV) at 339.96 oC. The
43 10 percentage of residual mass at 500 oC is 16.52 %. The chemical structure and composition of epoxy resin DER
44
11 671X75 and the modified phenolic T31 curing agent have many aromatic rings, so epoxy polymer composite
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12 material DER 671X75/T31 has high thermal stability. Epoxy polymer composite material DER 671X75/T31 is a
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47 cross-linked thermosetting resin structure. The chemical structure and cross-linking density of epoxy polymer
48 14 composite DER 671X75/T31 are the factors that make up thermal stability [25].
49 15 On the DSC from Figure 2, the glass transition temperature Tg is about 190 oC due to the high crosslinking density
50 16 and many aromatic rings in the epoxy composite structure DER 671X75/T31. The Tg marks a polymer’s transition
51 17 from an amorphous glass to a rubbery solid and defines the limits of processability for most polymer. The peak at
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18 69.22 oC represents the loss of the volatile component which acetone solvent is used to adjust the viscosity of epoxy
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54 19 resin DER 671X75 curing with T31. The process of solvent evaporation in the sample continues to occur up to a
55 20 temperature of 150-158 oC. The epoxy polymer sample DER 671X75/T31 is completely cured 100 % at the peak of
56 21 234 oC on the DSC curve. On the DSC curve, there are also other peaks at 374.11 oC, 484.61 oC, and 618.13 oC,
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3 1 which also show that the thermal decomposition of the sample continues or can be the instability of the DSC’s
4 2 baseline.

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3 The TG-DSC thermal analysis diagram of epoxy composite polymer material DER 671X75/5 % triphenyl
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4 phosphate/T31 is shown in Figure 3:
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Figure 3. TG-DSC thermal analysis diagram of epoxy composite polymer DER 671X75/ 5 % triphenyl phosphate/T31

The TG-DSC thermal analysis results of epoxy polymer composite material DER 671X75/5 % triphenyl
phosphate/T31 are presented in Table 3:
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8 Table 3. TG-DSC thermal analysis results of epoxy polymer composite material DER 671X75/5 % triphenyl
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30 9 phosphate/T31
31 10
Sample Temperature (°C) TG |rs |s (%) HeatFlow |-bs |s (µV)
32 11
33 12 31.52888 100 0
34 13 64.93263 100.0023 -0.59279
35 14 158.4032 99.00133 -0.13386
36
37
15 160.915 98.93986 -0.15318
38 16 187.5381 98.2471 -0.00223
17
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39 200.0152 97.92179 0.238481

40 18 345.0716 86.05397 2.222902
41 19 375.5703 68.58176 -3.16443
42 20
43 430.5829 39.04512 -31.3822
21
44 500.0577 28.2967 -1.24224
45
22
46 23 The results from the TG-DSC thermal analysis diagram in Figure 3 and Table 3 show that the starting decomposition
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47 24 temperature of epoxy polymer DER 671X75/5 % triphenyl phosphate/T31 is about 158-187 oC. The strongest
48 25 decomposition temperature corresponds to the peak with the largest energy on the DSC curve at 345.07 oC
49 26 (HeatFlow 2.222902 µV). The percentage of residual mass at 500 oC is 28.29 %.
50 27 The results from Figure 2, Figure 3, Table 2, and Table 3 show that the thermal stability of epoxy polymer composite
51
28 material DER 671X75/5 % triphenyl phosphate/T31 is better than epoxy polymer composite material DER
52
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53 29 671X75/T31, with the highest decomposition temperature increases from 339.96 oC to 345.07 oC. Thus, triphenyl
54 30 phosphate with a content of 5 wt % increases the thermal stability of the epoxy polymer DER 671X75/T31.
55 31 Triphenyl phosphate has the following chemical formula (Figure 4).
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58 7
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4

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10
11
12 Figure 4. Chemical formula of triphenyl phosphate (TPP)
13 1
14 2 Triphenyl phosphate (TPP) with chemical formula is shown in Figure 4 that consists of three aromatic rings around
15 3 the phosphate group. The aromatic rings in triphenyl phosphate are chemically resistant to thermal stability. So,
16 4 triphenyl phosphate is enhanced for the epoxy polymer composite DER 671X75/T31, the thermal stability of epoxy

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17 5 composite material DER 671X75/triphenyl phosphate/T31 is better. According to the study [21], triphenyl phosphate
18 6 was completely decomposed with the heat starting at around 200 oC. The mechanism of heat stability, fire resistance
19 7 of triphenyl phosphate mainly took place in the gas phase, under the effect of temperature, triphenyl phosphate
20
8 would decompose to create free radicals PO• , PO 2 • , and was able to capture free radicals H • , OH • , generated in
21
22 9 the combustion process, thereby reducing the number of active centers that affected on the development of
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10
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combustion of the material. Triphenyl phosphate also contributed to the solid-phase fire resistance mechanism. In the
thermal decomposition process, triphenyl phosphate could form a protective thin solid layer covering the surface of
the material, which played the role of preventing the release of the products produced in the polymer degradation
process and preventing diffusion of oxygen into the burning zone [30-31].
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29 15 3.2. Effects of nanosilica and triphenyl phosphate on the mechanical properties, thermal stability of epoxy
30 16 polymer composite DER 671X75/nanosilica/triphenyl phosphate/hardener T31
31 17 3.2.1. Mechanical properties of epoxy polymer composite coating film DER 671X75/nano silica/triphenyl
32 18 phosphate/T31
33
19 Nanosica (fumed silica S5505) with a content of 1 wt % is dispersed in epoxy resin DER 671X75. The TEM image
34
35 20 of epoxy nanocomposite material DER 671X75/1 % nanosilica/T31 is shown in figure 5:
36
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52 Figure 5. TEM image of epoxy nanocomposite DER 671X75/1% nanosilica (fumed silica S5505)/T31
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53 21
54 22 The TEM image from Figure 5 shows that nanosilica (fumed silica S5505) is well dispersed in epoxy resin DER
55 23 671X75/T31 to form a nanocomposite structure. Nanosilica particles are dispersed into epoxy resin DER 671X75.
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3 1 However, nanosilica particles tend to combine, there are regions of the nanosilica particles with an average size of
4 2 about 10-20 nanometers. These result are similar to other studies [23, 25, 32]. Due to the high surface activity is

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5
3 formed by the bonds of the Si-O group, adjacent nanosilica particles tend to gather and cluster together to form larger
6
7
4 size particles.
8 5 The mechanical properties of epoxy coating films DER 671X75/1 % nanosilica /5 % triphenyl phosphate/T31 are
9 6 presented in Table 4:

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10 7 Table 4. Mechanical properties of epoxy coating films
11 Dry film Impact
12 Sample Composition thickness strength
Flexibility Pencil
Adhesion
13 (mm) hardness
(µm) (kG.cm)
14
15 E0 Epoxy DER 671X75/T31 76.23 20 2 5H 5B
16 Epoxy DER 671X75/5 %

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E5TPP 83.28 25 2 5H 5B
17 triphenyl phosphate/T31
18 Epoxy DER 671X75/5 %
19 E5TPPSi triphenyl phosphate /1 % 78.5 45 2 5H 5B
20
nanosilica/T31
21
22 8 The results from Table 4 show that the mechanical properties of epoxy coating film DER 671X75/ 1% nanosilica/5
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13
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% triphenyl phosphate/T31 significantly increase the impact strength of polymer coating film from 20 kG.cm to 45
kG.cm (increased by 125 %). According to the study [25], the content of 1 wt % nanosilica also increased the
mechanical properties of epoxy coating film DER 671X75/Epicure 3215. It can be seen that nanosilica with a content
of 1 wt % improves compatibility triphenyl phosphate with epoxy resin DER 671X75 and nanoparticles nanosilica
with a characteristic of nano size and high surface activity that increases the interoperability with epoxy resin,
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29 14 thereby the toughness of epoxy polymer coating film DER 671X75/1 % nanosilica/5 % triphenyl phosphate/T31
30 15 (E5TPPSi sample) is improved.
31 16 3.2.2. Thermal stability of epoxy polymer composite material DER 671X75/triphenyl phosphate/
32 17 nanosilica/hardener T31
33 18 The TG-DSC thermal analysis diagram of epoxy polymer composite material DER 671X75/1 % nano silica/5 %
34
19 triphenyl phosphate/T31 (E5TPPSi sample) is shown in Figure 6:
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Figure 6. TG-DSC thermal analysis diagram of epoxy polymer composite material
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53 DER 671X75/1 % nano silica/5 % triphenyl phosphate/T31

20
54 21 The TG-DSC thermal analysis results of epoxy polymer composite material DER 671X75/1 % nanosilica/5 %
55 22 triphenyl phosphate/T31 are presented in Table 5:
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3 1 Table 5. TG-DSC thermal analysis results of epoxy polymer composite material DER761X75/1 % nanosilica/5 %
4 2 triphenyl phosphate/T31

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6 Sample Temperature (°C) TG |rs |s (%) HeatFlow |-bs |s (µV)
7 28.07195 100 0
8 69.17218 100.0009 -0.4038
9

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210.0228 99.03637 0.442051
10
11 214.1854 99.00013 0.504626
12 297.5617 98.37627 -0.90426
13 312.2277 98.00222 -0.47729
14
494.1214 19.56637 2.386507
15
16 500.0612 19.34543 2.184209

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17 600.0153 16.83253 0.273688
18 3 The TG-DSC thermal analysis results from Figure 6 and Table 5 show that the starting temperature decomposition of
19 4 epoxy polymer composite material DER 671X75/1 % nanosilica/5 % triphenyl phosphate/T31 is about 210-214oC.
20
5 The strongest decomposition temperature corresponds to the peak with the largest energy on the DSC curve at the
21
22 6 temperature of 494.12 oC (HeatFlow 2.386507 µV). The percentage of residual mass at 500 oC is 19.34 %.
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The above results show that the thermal stability of the epoxy polymer composite material DER 671X75/T31 in
ascending order is E0, E5TPP, E5TPPSi samples. The starting of decomposition temperature, as well as the strongest
decomposition temperature of epoxy polymer DER 671X75/T31 gradually increases from 339.96 oC (E0 sample),
increases to 345.07 oC (the content of 5 wt % triphenyl phosphate, E5TPP sample), and increases to 494.12 oC (up
45.35%, content of 5 wt % triphenyl phosphate and 1 wt % nanosilica, E5TPPSi sample). Nanosilica with a content
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12 of 1 wt % increased thermal stability of the epoxy composite polymer material DER 671X75/Epicure 3125 [25].
30 13 Nanocomposite/nanosilica increases the thermal stability because polymer molecules encapsulate with nanosilica
31 14 particles and nanosilica particles act to prevent the diffusion of oxygen necessary for polymer combustion. In
32 15 addition, nanosilica particles also play a role in keeping heat and hindering the release of volatile products when the
33 16 polymer burns. So, the combination of triphenyl phosphate and nanosilica in nanocomposite material significantly
34 17 increases the thermal stability of epoxy polymer composite material DER 671X75/T31.
35
18
36
37 19 3.3. Effects of nanosilica and triphenyl phosphate on the mechanical properties, thermal stability of epoxy
38 20 coating
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39 21 The coating based on epoxy resin DER 671X75 (PE5TPPSi) is manufactured with the composition in Table 6.
40 22 The components in the PE5ZBSi epoxy coating in Table 6 include epoxy resin DER 671X75, triphenyl phosphate,
41 23 nanosilica, pigments, fillers, additives, solvents, and hardener T31. Epoxy paint is used to protect anti-corrosion for
42 24 steel structures and heat equipment, so in the paint composition used filler pigment system with corrosion resistance
43
25 and heat resistance. In which, the composition of iron oxide pigment, talc filler, pigment inhibited zinc phosphate
44
45 26 corrosion process similar to research results of the study [33]. Other components in the PE5ZBSi epoxy coating
46 27 include Troysperse CD1 as a general-purpose polymeric pigment dispersant and wetting additive for non-aqueous
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47 28 systems. Crayvallac super is a high performance, micronized amide wax rheology modifier suitable for a wide range
48 29 of solvent-based, high-solids, and solvent-free applications. The plasticizer of dioctyl phthalate (DOP) improves the
49 30 toughness and flexibility of epoxy coating films. Nanosilica (fumed silica S5505) reinforces the mechanical
50 31 properties, anti-corrosion, and increases thermal stability for paint [25, 32, 33]. Triphenyl phosphate (TPP) enhances
51
52
32 the mechanical properties and thermal stability of epoxy coating films. A mixture of solvents is xylene, toluene,
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53 33 acetone for adjusting viscosity, volatility, and drying time of the coating film. Curing for epoxy coating uses a T31
54 34 curing agent according to the ratio of epoxy resin DER 671X75/hardener T31: 100/30 (wt/wt).
55 35
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3 1 Table 6. Epoxy coating composition
4

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Epoxy coating Composition Weight
5
PE5TPPSi (%)
6
7 Epoxy resin DER 671X75 100
8 Nanosilica (fumed silica S 5505) 1.0
9 Iron oxide 75

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10 Zinc phosphate 60
11 Talc filler 15
12
Troysperse CD1 1.5
13 Part A
14 Plastilizer dioctylphtalate (DOP) 8
15 Crayvallac super 1
16 Triphenyl phosphate (TPP) 5

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17 Xylene 52.5
18 Toluene 15
19 Acetone 7.5
20
21 Part B Hardener T31 30
22 2 Some physical chemistry properties of epoxy coating DER 671X75 and mechanical properties of the coating are
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3
4
presented in Table 7:

Sample
Dry film Impact
thickness strength
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Table 7. Mechanical properties of epoxy coating film and epoxy coating DER 671X75/T31

Flexibility Pencil
Grinding
Adhesion fineness
Viscosity
Dried time
(hrs)
Tack- Dry-
dM
(mm) hardness (second)
29 (µm) (kg.cm) (µm) free hard
30 time time
31 PE5TPPSi 88.35 50 2 5H 5B 25 32 2 6
32
33
5 The epoxy coating DER 671X75/T31 has the composition of iron oxide pigment system, zinc phosphate, talc filler,
34 6 and other components according to Table 6. Epoxy paint is milled in a ball mill for 8 hours to reach the grinding
35 7 fineness of 25 µm. The measured results in Table 7 show that epoxy coating DER 671X75/T31 obtains all the
36 8 necessary properties for steel protection coating.
37 9 The TG-DSC thermal analysis diagram of epoxy coating DER 671X75 is shown in Figure 7:
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55 Figure 7. TG-DSC thermal analysis diagram of epoxy coating DER671X75/T31
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3 1 The TG-DSC thermal analysis results of epoxy coating DER 671X75 are presented in Table 8:
4 2 Table 8. TG-DSC thermal analysis results of epoxy coating DER 671X75

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6 Sample Temperature (°C) TG |rs |s (%) HeatFlow |-bs |s (µV)
7 29.18078 100 0
8 174.3705 99.271 -0.00254
9

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189.2832 99.00068 0.081425
10
11 200.0064 98.79469 0.176631
12 249.4915 98.00032 1.046016
13 319.2277 94.23966 3.976011
14
362.5306 83.27471 1.767974
15
16 500.0042 58.06227 5.618408

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17 524.3116 56.86723 6.810669
18 600.0619 53.40423 2.852022
19
3 The results from Figure 7 and Table 8 show that the starting temperature decomposition of epoxy coating DER
20
21
4 671X75/T31 (PE5TPPSi) is about 210-249 oC. The strongest decomposition temperature of the paint sample
22 5 corresponds to the peak with the largest energy on the DSC curve is 524.31o C (HeatFlow 6.810669 µV). The
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6
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percentage of residual mass at 500 oC is 58.06 %. The thermal stability of the PE5TPPSi epoxy coating due to
chemical structure and composition of epoxy based on resin DER 671X75/curing agent phenolic modified amine
T31, the paint is enhanced by iron oxide pigment system, talc filler, zinc phosphate corrosion inhibiting pigment,
nanosilica, and triphenyl phosphate. The components in the PE5TPPSi epoxy coating have the effect of thermal
stability, also increase anti-corrosion of the coating.
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29 11 The thermal degradation of epoxy polymer composite materials DER 671X75/T31 and epoxy coating DER
30 12 671X75/T31 are summarized and presented in Table 9:
31 13 Table 9. Thermal degradation of epoxy polymer composite materials DER 671X75/T31
32 The starting The strongest Percentage of
33 decomposition decomposition residual mass at
34 Sample Composition
temperature temperature 500 oC
35 o o
36 ( C) ( C) (%)
37
38 E0 Epoxy DER 671X75/T31 150-158 339.96 16.52
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40 Epoxy DER 671X75/5 % triphenyl
E5TPP 158-187 345.07 28.29
41 phosphate/T31
42 Epoxy DER 671X75/5 % triphenyl
E5TPPSi 210-214 494.12 19.34
43 phosphate/1 % nanosilica/T31
44 Epoxy coating DER 671X75/5 %
45 PE5TPPSi triphenyl phosphate/1 % 210-249 524.31 56.86
46
nanosilica/pigments/fillers/T31
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48 14 The results from Table 9 show that polymer composite materials and epoxy coating based on epoxy resin DER
49 15 671X75/T31 have high thermal stability. The thermal stability of samples increases gradually in the order of samples
50 16 E0, E5TPP, E5TPPSi, PE5TPPSi. In particular, epoxy nanocomposite materials DER 671X75 reinforce with the
51 17 content of 1 wt % nanosilica and content of 5 wt % triphenyl phosphate, the thermal stability increases significantly
52 18 with the strongest decomposition temperature increases from 339.96 oC to 494.12 oC (increased 45.35 %) and epoxy
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19 coating PE5TPPSi is 524.31 oC (increased 54.23 %) that indicating potential application for high thermal resistant
55 20 epoxy paints above 500 oC.
56 21
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3 1 4. CONCLUSIONS
4 2 The mechanical properties of the epoxy composite coating film DER 671X75/hardener T31 increased with a content

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3 of 5 wt % triphenyl phosphate, the impact strength increased from 20 kG.cm to 25 kG.cm (increased 25 %). The
6
7
4 impact strength of epoxy polymer composite coating film DER 671X75/5 % triphenyl phosphate/1 % nanosilica/T31
8 5 increased from 20 kG.cm to 45 kG.cm (increased 125 %). The thermal stability of epoxy polymer composite material
9 6 increased according to the order of epoxy DER 671X75/T31, epoxy DER 671X75/ 5 % triphenyl phosphate/T31,

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10 7 epoxy DER 671X75 /1 % nanosilica/5 % triphenyl phosphate/T31. The thermal stability of epoxy nanocomposite
11 8 material DER 671X75/1 % nanosilica/5 % triphenyl phosphate/T31 increased by 45.35 %. The epoxy coating based
12 9 on epoxy resin DER 671X75/T31 was reinforced with a content of 1 wt % nanosilica, 5 wt % triphenyl phosphate
13
10 and pigments, additives achieved mechanical properties, physical chemistry properties for coating, and had thermal
14
15 11 degradation over 500 oC.
16 12

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17 13 ACKNOWLEDGMENTS
18 14 This work was supported by Ho Chi Minh City University of Food Industry (HUFI) (Contract No 41/HĐ-DCT dated
19 15 9/9/2020).
20 16
21
22
17 DATA AVAILABILITY STATEMENT
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All data that support the findings of this study are included in the article.

ORCID IDS: Cuong Huynh Le Huy https://orcid.org/0000-0002-8015-7678

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