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Progress in Organic Coatings 77 (2014) 949–956

Contents lists available at ScienceDirect

Progress in Organic Coatings

j o ur na l ho me pa ge: www.elsev ier .com/ locate /porgcoat

reparation and characterization of water reducible alkydesin/colloidal silica nanocomposite coatings

˙lhan Kurt, Is ıl Acar, Gamze Güc lü ∗

epartment of Chemical Engineering, Faculty of Engineering, Istanbul University, Avcılar, Istanbul 34320, Turkey

r t i c l e i n f o

rticle history:eceived 14 June 2013eceived in revised form 13 January 2014ccepted 15 January 2014vailable online 10 February 2014

a b s t r a c t

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthe-sized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was preparedwith tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resinwas neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butylglycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resinwas diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to

eywords:lkyd resinolloidal silicaanocompositeater reducible alkyd

ilm propertiesurface coating material

prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silicananoparticle addition on the surface coating properties, thermal behaviors and surface morphologies ofwater reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improvedsurface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.

© 2014 Elsevier B.V. All rights reserved.

. Introduction

Alkyd resins are condensation polymers of dibasic acids, poly-ydric alcohols and fatty acids. The name “alkyd” comes from its

ngredients; alcohols and acids. These resins are polyesters modi-ed with monobasic fatty acids [1]. Alkyds are fundamental binderaterials for the manufacture of different types of surface coating

2]. Alkyds have been a part of the coating industry since 1926 [3].lkyd based coatings have good surface coating properties such asood corrosion protection, high gloss, fast dryness, and these resinsave good interactions with polar substrates such as wood and steel3–5]. The coatings of standard conventional alkyds are solventased resins, and these resins are diluted with an organic solventuch as toluene, xylene, white spirit and a mixture of these solvents5]. The emission of toxic volatile organic compounds (VOC) duringhe application and curing process from solvent based alkyd resinsauses many environmental problems [5,6]. In order to overcomehese disadvantages of alkyds, two different types of alkyd resinsere developed. These resins are acrylic modified alkyd emulsions

nd water reducible alkyd resins [5,7,8]. Acrylic modified alkyd

mulsions were synthesized with different techniques. For exam-le, the blending of an alkyd with an acrylic dispersion is preparedy emulsification of an alkyd in the presence of an acrylic dispersion

∗ Corresponding author. Tel.: +90 212 473 70 70; fax: +90 212 473 71 80.E-mail address: gguclu@istanbul.edu.tr (G. Güc lü).

300-9440/$ – see front matter © 2014 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.porgcoat.2014.01.017

[7] or carboxy-functional acrylic copolymer is used for preparationof an alkyd resin such as a dicarboxylic acid component [8]. Alkydresins with high acid values can be made water reducible by neu-tralization of their free carboxyl groups with amine compoundssuch as triethylamine, diethanolamine [9–12]. Compared to theirsolvent-based counterparts, these resins have many advantagessuch as lower VOC, reduced odor, and lower flammability [12].

In recent years, organic–inorganic nanocomposites haveattracted attention in various fields such as material science, paints,high-quality paper coatings, electronics, cosmetics and biotech-nology because of their excellent performances compared toconventional materials [13–15]. Nanotechnology is also extremelyimportant for the paint industry [16]. The inorganic nanoparticlesused for the polymeric coatings are SiO2, TiO2, Al2O3, CaCO3, ZnO,Fe2O3 and organo clay [17–25]. Especially silica based nanocom-posites are widely used in coatings for the improvement of waterresistance, mechanical and thermal properties of resins [26,27]. Forexample, Ye et al. synthesized nano-silica/polyacrylate compositeemulsions via in-situ emulsion polymerization technique [26]. Zhuet al. used the suspension-dispersion-polymerization method toprepared poly(styrene-buthylacrylate-acrylic acid)-grafted-silicananocomposites. The Authors reported that nanocompositescontaining 1.5 wt.% silica showed a significant improvement in

adhesion properties, mechanical properties and UV and waterresistance of films [27]. Wada et al. prepared composite materialsfrom acrylic resin emulsions and colloidal silica by emulsionpolymerization [15]. Is ın et al. and Jacquelet et al. investigated the

9 anic Coatings 77 (2014) 949–956

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Table 1Symbols and properties of alkyd resins.

Symbols of alkyd resins Solid content (wt.%) Colloidal silicaratio (wt.%)

Stock alkyd resin (SA) 75 –WRAR (reference resin) 50 0WRAR-5 50 5WRAR-10 50 10WRAR-15 50 15WRAR-20 50 20

Table 2Properties of stock alkyd resin.

Properties of stock alkyd resin

Solid content 75 wt.%

film. The oscillations of a standardized König pendulum placed on

50 I. Kurt et al. / Progress in Org

reparation and characterization of epoxy/silica and polyester/elamine-pyrogenic silica nanocomposite coatings, respectively

14,16].As shown in this literature survey, there are many studies on

anocomposite coatings containing silica and there are severalapers about modified alkyd resins with nano particles such asinc oxide, iron oxide titanium dioxide, silica and organo clay18–20,28–31]. In previous work, we also investigated preparationnd film properties of alkyd-melamine formaldehyde resin con-aining colloidal silica [22]. A literature survey has not yielded anyesearch on the water reducible alkyd resins containing colloidalilica.

In the present study, water reducible alkyd resins containingifferent amounts of colloidal silica were synthesized for the firstime. Then the effect of a silica nanoparticle addition on the surfaceoating properties, thermal behaviors and surface morphologies ofater reducible alkyd resins was investigated.

. Experimental

.1. Materials

Tall oil fatty acid (TOFA) was used in the preparation of alkydesins. TOFA [Sylfat 2S, iodine value (IV) 155, acid value (AV)97] was obtained from Arizona Chemicals (USA). Trimethylol-ropane (TMP) and isophthalic acid (IPA) were obtained fromerstorp (Sweden). Trimellitic anhydride (TMA) was obtained fromP Chemical (Korea). Colloidal silica suspension (50% wt., LUDOXM-50) was obtained from Sigma–Aldrich (USA). The rest of theaterials were obtained from Merck (Germany). Drier for water

ased coatings (ready-to-use cobalt/zirconium/lithium water mis-ible drier combination; Nuodex Combi Web Aq) was obtained fromktif Kimya (Turkey). All solutions were prepared to use deionizedater.

.2. Preparation of water reducible alkyd resins containingolloidal silica

Alkyd formulated to have oil content 35% was prepared withOFA, IPA, TMA, TMP. “K alkyd constant system” was used for theormulation calculations of the alkyd resins [32]. The K constantas 1, and the ratio of basic equivalents to acid equivalents (R)as 1.32. The reaction was carried out in a round bottom flask

quipped with a Dean–Stark piece, gas bubbler, contact thermome-er and mechanical stirrer system. TOFA, IPA, TMP were chargedo the flask and the system heated to 200 ◦C. Azeotropic solventylene was added to the reaction mixture, and the reaction mix-ure was heated to 250 ◦C. Then, the temperature of the reactionas kept constant at 240–250 ◦C. The reactions were followed with

cid value (AV). Condensation reaction was allowed to continuentil the acid value of the resin was approximately 10 mgKOH/g.he acid values were determined by titration of samples dissolvedn ethanol–toluene with 0.1 N KOH solution. Then, the temperature

as reduced to 150 ◦C, and TMA was added to the reaction mixturend the temperature was raised to 185 ◦C. Reaction was allowed toontinue until the acid value of the resin was 50 mgKOH/g. Then, thelkyd resins were neutralized with triethylamine (TEA) at 120 ◦C.he alkyd resin was dissolved in isobutyl alcohol-isopropyl alcohol-utyl glycol mixture to produce 75% (wt.) solution which is calledtock alkyd resin (SA). The pH was adjusted to slightly alkalinepH 8.3) with 25% ammonia solution. The stock alkyd resin was

iluted with water to 50% (wt.) concentration [11,33]. Then, waternd a colloidal silica mixture were added, and the solution wasgitated vigorously. Thus, alkyd solutions which are solid contentf 50% (wt.) containing 0%, 5%, 10%, 15% and 20% colloidal silica

Acid value 50 mg KOH/gViscosity (determined by Gardner Bubble Tube) 92 s

were prepared with colloidal silica and a distilled water mixture.The symbols and properties of water reducible alkyd resin (WRAR)containing colloidal silica were given in Table 1.

In addition, properties of SA such as solid content, acid value andviscosity were given in Table 2. The viscosity of SA was determinedby a Gardner Bubble Tube according to the Gardner-Holdt method,which had been given in ASTM D-1545.

2.3. Scanning electron microscope (SEM) analysis

The scanning electron micrographs of the resins were taken atdifferent magnification of with a FEI Quanta FEG 450 SEM with anEDAX energy dispersive X-ray analytical system.

2.4. Thermogravimetric analysis (TGA)

Thermogravimetric analysis (TGA) was carried out by LinsesisSTA PT 1750 model under air at a rate of 10 ◦C/min with about 20 mgof resins.

2.5. Film properties of water reducible alkyd resins

WRAR films, which contain 2% drier, were prepared for physicaland chemical surface coating tests. The films cast by 50 �m applica-tors from the solutions were dried at 25 ± 1 ◦C for 72 h (air dried). Inaddition, some of the films were oven cured at 150 ◦C for 1 h (ovencured).

2.5.1. Physical film properties of water reducible alkyd resinsDrying time was determined by an Erichsen 415/E apparatus,

which gave results according to DIN 53150. Determination of dry-ing time of the resins is estimated by adherence or non-adherenceof paper or glass beads. There are seven drying stages of thismethod, and the maximum drying degree is 7. Stage 1 is deter-mined with glass beads, and the remaining stages are determinedwith disks of typewriter paper (loads range from 5 to 5000 g/cm2).The glass beads are allowed to remain on film for 10 s, and the loadson the disks remain for 60 s [30,34].

Hardness was determined by König Pendulum, which gaveresults according to the DIN 53 157 standard. The procedure ofhardness determination with König Pendulum is based on the mea-surement of the damping of a pendulum oscillating on the paint

the test surface are damped in proportion to the “softness” of thecoating [30,34].

Adhesion strength of the films was determined by the cross-cutmethod according to ASTM D 3359-76.

I. Kurt et al. / Progress in Organic Coatings 77 (2014) 949–956 951

Table 3Drying test results of WRAR films.

Alkyd resins Dry-to-touch (h) Drying degree

Air drieda Oven curedb

WRAR 3 4 7WRAR-5 3 4 7WRAR-10 3 4 7WRAR-15 3 4 7WRAR-20 3 4 7

a After 72 h.b 1.5 h at 150 ◦C.

Table 4Hardness test results of WRAR films.

Alkyd resins Hardness (König second)Air drieda Oven curedb

WRAR 39 158WRAR-5 40 150WRAR-10 41 140WRAR-15 42 120WRAR-20 42 73

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Fig. 1. SEM micrograph of WRAR (reference resin) with 60.000 magnification.

a After 72 h.b 1.5 h at 150 ◦C.

Abrasion resistance was determined by an Erichsen Send Abra-ion Tester, type 2511-11, which gave results according to ASTM

968-05. Abrasion resistance is usually performed with a fallingand abrasion test. Sand is dropped down a vertical tube onto theanel that is mounted at a 45◦ angle. The results are given as themount of sand required removing a certain thickness of coating30].

The impact resistances of films were determined according toSTM D 2794-69 standard. This test was applied using FTMS 6226

mpact flexibility tester which determines failure between 0.5 and0% elongation of the film after impact [30,34].

The glosses of the resins were measured with a Gardner Mul-iangle Glossmeter (Model GG 9095) at a 45◦ angle, which gaveesults according to ASTM D523 [30,34].

.5.2. Chemical film properties of water reducible alkyd resinsThe effect of water immersion (water resistance) was deter-

ined according to ASTM D1647. WRAR films were prepared on tinanels for this test. Then these panels were immersed in water for8 h. The appearances of the films were determined immediatelyfter wiping dry, 20 min, 1 h and 2 h later [30].

The alkaline, acid resistance and salt water resistance determi-ations were carried out according to ASTM D1647. WRAR filmsere prepared on glass test tubes for this test. Then, the tubes were

mmersed in alkaline (3% wt. NaOH and 0.1 M NaOH), acid solutions

3% wt . H2SO4) or salt water solutions (5% wt. NaCl). The tubes wereemoved from the solutions after immersion for 1, 2, 3, 5, 7, and 24 hnd the appearances of the films were observed [30].

able 5brasion resistance, adhesion, impact resistance and gloss tests results of WRARlms.

Abrasionresistance(mL sand)

Adhesion (%) Impactresistance(%)

Gloss

WRAR 800 100 >60 92WRAR-5 800 100 >60 87WRAR-10 850 100 >60 80WRAR-15 900 100 >60 68WRAR-20 1000 100 >60 40

Fig. 2. SEM micrographs of WRAR-10. (a) with 30,000 magnification (b) with130,000 magnification.

952 I. Kurt et al. / Progress in Organic Coatings 77 (2014) 949–956

Fig. 3. EDAX spectrum of WRAR-10.

Table 6Water, acid and salt water resistance tests results of WRAR films.

Water resistance(effect of 18 hwater immersion)

Acid resistance(3% H2SO4 for24 h)

Salt waterresistance (5%NaCl for 24 h)

WRAR NC NC NCWRAR-5 NC NC NCWRAR-10 NC NC NCWRAR-15 NC NC NCWRAR-20 NC NC NC

NC: no change.

The solvent resistance tests of WRAR films were also doneaccording to the procedure which is given below [35]. The filmswere prepared on glass panels for this test. A piece of solvent-impregnated (acetone, methanol, toluene and ethyl acetate)absorbent gauze (2 × 2 cm) was put on the resin coated glass panel.The panel was covered with a petri dish, and it kept at room tem-perature for 30 min. The end of the test the appearances of films

were evaluated visually.

All tests were repeated three times to confirm the repeatabilityof the tests.

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I. Kurt et al. / Progress in Org

. Results and discussion

Alkyd solutions containing 0%, 5%, 10%, 15% and 20% colloidalilica were prepared using stock alkyd resin, colloidal silica andistilled water. Surface coating properties of WRAR were deter-ined according to related ASTM standards. Surface morphologies

nd thermal behaviors of these were investigated by SEM and TGAnalyses.

.1. Surface coating properties of water reducible alkyd resins

The results of drying degree test of all WRAR films were givenn Table 3. Before this test was applied, it was investigated if thelms had reached the “dry-to-touch” stage or not. As known, “dry-o-touch” stage is defined as when no mark is left when the film isouched by a finger [36]. As seen from the table, all WRAR filmseached “dry-to-touch” stage at the end of 3 h. While air dried

RAR films reached to stage 4 at the end of 72 h, all WRAR filmseached to stage 7 after being oven cured. As a result, colloidal sil-ca has not shown a negative effect on drying degree and it has notaused a significant change of drying time.

ig. 4. SEM micrographs of WRAR-20. (a) with 30,000 magnification (b) with30,000 magnification

oatings 77 (2014) 949–956 953

Hardness test results were given in Table 4 as König second forair dried and oven cured WRAR films. As seen from the table, hard-ness values of air dried films were approximately determined as40 s. In the case of oven cured WRAR films, hardness values of thesewere also determined as 158, 150, 140, 120 and 73 König secondfor WRAR, WRAR-5, WRAR-10, WRAR-15, WRAR-20, respectively.

When the results of drying degree and hardness tests were eval-uated together, it is seen that, air dried WRAR films could not reachthe desired drying degree. In parallel with, low hardness valueswere obtained for air dried WRAR films. According to these results,surface coating tests were applied to oven cured WRAR films.

The results of adhesion, abrasion resistance, impact resistanceand gloss tests of oven cured WRAR films were given together inTable 5. As seen from Tables 4 and 5 while hardness values of WRARfilms were decreased with increasing of colloidal silica, abrasionresistance of these films increased. As a result, WRAR films gainedelasticity due to the increasing of colloidal silica amounts. This sit-uation may have arisen from Si O Si bonds in the alkyd structure.This formation is explained below: Hydrogen bonds occurred fromthe interaction between the free hydroxyl groups on the surface ofthe hydrate colloidal silica particles and free hydroxyl groups of thealkyd resin structure [37]. Thus, Si O Si bonds in the silica haveincorporated alkyd structure.

As seen in Table 5, all of the WRAR films had excellent adhesionproperties (100%) and impact resistance (>60). As expected, glossvalues of WRAR films were decreased with increasing colloidal sil-ica amounts (Table 5). In case of colloidal silica addition of up to 15%,these films still conserve their properties of glossy surface coatingmaterials. However, in case of 20% colloidal silica content, WRARfilm gained a semi-glossy property.

Water, acid and salt resistance tests results of WRAR filmswere given in Table 6. In addition, alkaline resistance tests resultsof WRAR films were given in Table 7. As seen from Table 6, allWRAR films showed excellent water, acid and salt water resis-tance. According to both alkaline resistance test results, 20% wt.colloidal silica content has improved alkaline resistance of WRARfilm (Table 7). Solvent resistances of WRAR films were given inTable 8. As seen from the table, in case of 15% and 20% of colloidalsilica content, solvent resistance properties of WRAR films havebeen excellent for all solvents.

3.2. SEM analysis

Surface morphologies of WRAR, WRAR-10 and WRAR-20 wereinvestigated with the SEM and EDAX analysis. SEM micrographsand EDAX spectrums of the resins were illustrated in Figs. 1–5.

Table 7Alkaline resistance tests results of WRAR films.

Alkaline resistance NaOH 3%

15 min 30 min 1 h 1.5 h 2 h

WRAR S PD D D DWRAR-5 S PD D D DWRAR-10 S PD D D DWRAR-15 S PD D D DWRAR-20 SB PS PD D D

Alkaline Resistance 0.1 M NaOH

15 min 30 min 1 h 1.5 h 2 h

WRAR SB PS S PD DWRAR-5 SB PS S PD DWRAR-10 SB PS S PD DWRAR-15 SB PS S PD DWRAR-20 NC NC PS S PD

NC: no change; SB: slightly blurry; PS: partial swelled; S: swelled; PD: partial detach-ment; D: detachment.

954 I. Kurt et al. / Progress in Organic Coatings 77 (2014) 949–956

Fig. 5. EDAX spectrum

Table 8Solvent resistance test results of WRAR films.

Solvents

Methanol Ethyl acetate Acetone Toluene

WRAR PS PS PS PSWRAR-5 PS PS PS PSWRAR-10 PS PS PS PS

N

AmiomWr

WRAR-15 NC NC NC NCWRAR-20 NC NC NC NC

C: no change; PS: partial swelled.

s seen in Fig. 1, surface of the WRAR is smooth. However, SEMicrographs of WRAR-10 and WRAR-20 showed that colloidal sil-

ca particles have dispersed into alkyd resin (Figs. 2 and 4). It is

bserved that colloidal silica particles were embedded in the poly-er matrix in all micrographs. EDAX spectrums of WRAR-10 andRAR-20, which is given in Figs. 3 and 5, have also confirmed these

esults.

of WRAR-20.

3.3. TGA analysis

Thermal oxidative degradations of WRAR films were investi-gated by TGA under air atmosphere at a heating rate of 10 ◦C min−1.TGA curves were presented in Figs. 6–9. As seen in these figures, allresins show almost similar degradation behaviors. The temperaturevalues required for reaching to certain weight losses (20–80%) wereobtained from TGA curves are listed in Table 9. It can be said that, thecolloidal silica addition had increased thermal degradation stabilityof WRAR films according to these values. The temperature valuesrequired for reaching to 50% weight loss were 385, 393, 391, 394,403 for WRAR, WRAR-5, WRAR-10, WRAR-15, WRAR-20, respec-tively. As seen from Table 9, adding of colloidal silica nanoparticlescaused increasing the degradation temperature to 18 ◦C. While the

degradation temperature of WRAR at 80% weight loss is 436 ◦C,degradation temperature of WRAR-20 has been observed as 454 ◦C.As a result, incorporation of colloidal silica to the resin structuresignificantly increased the thermal stability of WRAR.

I. Kurt et al. / Progress in Organic Coatings 77 (2014) 949–956 955

Fig. 6. TGA curves of WRAR and WRAR-5 films.

Fig. 7. TGA curves of WRAR and WRAR-10 films.

Fig. 8. TGA curves of WRAR and WRAR-15 films.

Fig. 9. TGA curves of WRAR and WRAR-20 films.

Table 9The temperatures required for reaching to certain weight losses (%) of WRAR films.

Temperature (◦C)a

20% 30% 40% 50% 60% 70% 80%

WRAR 322 345 366 385 403 424 436WRAR-5 324 349 371 393 414 435 445WRAR-10 317 347 370 391 415 432 445WRAR-15 322 348 372 394 414 430 441WRAR-20 322 352 379 403 426 436 454

a The temperature where various weight loss has occurred.

4. Conclusions

In the present study, water reducible alkyd resins containingdifferent amounts of colloidal silica were synthesized for the firsttime. Then the effect of a silica nanoparticle addition on the surfacecoating properties, thermal behaviors and surface morphologies ofwater reducible alkyd resins was investigated.

The following conclusions can be drawn from the obtainedresults;

• Physical film properties: colloidal silica addition has not showna negative effect on drying degree of WRAR films. While hard-ness values of WRAR films were decreased with the increasingof colloidal silica, abrasion resistance of these films increased. Asa result, WRAR films gained elasticity due to the increasing ofcolloidal silica amounts. Further, all of the WRAR films had excel-lent adhesion properties and impact resistance. In addition, glossvalues of WRAR films were decreased with increasing colloidalsilica amounts and in case of 20% colloidal silica content, WRARfilm gained a semi-glossy property.

• Chemical film properties: all WRAR films showed excellent water,acid and salt water resistance. According to both alkaline resis-tance test results, 20% wt. colloidal silica content has improvedthe alkaline resistance of WRAR film. Moreover, in case of 15%and 20% of colloidal silica content, solvent resistance propertiesof WRAR films have been excellent for all solvents.

• Thermal properties: incorporation of colloidal silica to the resinstructure significantly increased the thermal stability of WRARfilms.

• Surface morphology: as seen from SEM micrographs and EDAXspectrum, colloidal silica particles dispersed into alkyd resinmatrix.

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In conclusion, nanocomposite water reducible alkyd resins inarious colloidal silica contents were successfully obtained in thistudy.

cknowledgement

This work is a master thesis titled “Preparation of watereducible alkyd resins containing nano particles and investigationf film properties”, which is prepared at Istanbul University in 2012.

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