Progress in Organic Coatings 59 2007 76:80 PROGRESS INORGANIC COATINGS wswavelseniersom locate paca Anticorrosive properties of the epoxy—cardanol resin based paints L.K. Aggarwal", P.C. Thapliyal, S.R. Karade Cental Buidng Rescurch laste, Roorkee 247607, laa Recehred Abstevet ptember 2006; accep 16 Januszy 2007 An epoxy-cardanol resin was developed using epiehoroiydrin, bisphenol and gardaol. On evaluation it was Fund that ¢puisy-eanda ‘esi exhibits better properties as compared to epoxy resin in terms of imerease in tensile strength, elas nt in| these properties tpdicate that the water Yapuur transmission oF align, bond with steel ain lowering vl mints based om modified resi yaad be mer sturable than the epoxy bused paints. Accordingly, paints were formulated using the developed resin and their performance were compared wath their counterparts made with unmodified epoxy sesin, Zine powd pigments along with fillers, additives and a were used, Physicosmechanical properties, chemical ‘was found that the anticontosive properties uf epony=ci ‘ine phaosphat aromatic polyamine adduct hardenes. For both types of pains sinilar deses of pigments ana stance and cortasion protection eflicieney of the formulated paitis were fanol resin bused puinls are superior £0 that of the paints Formulated wih the unislicd epoxy resin, Micaceous irom oxide based paints in epoay-cardanol resin showed the best perfor tide and synthetic nom oxide wore used ik di 1 followed by: ziae phosphate based pals. I 8 conetucled that the developed resin isa hetlerbindee media forthe formulation of pains 0 2007 Elsevier B.V. All rights reserved. Sexwunds: Epoxy: Cuidanol; Pigments Paints Permeability; Curosan: Chemical resistance 1. Introduction ‘The surveys of corrosion damage in the early. 1990s showed that in an industrialized country, 4% of the gross national prod luct (GNP) is lost us-a result of corrosion. This figure includes both direct and indirect costs [1}. The survey on causes of corra- sion failures has shown that over 40% of the failures are due to improperselection of materials, ineffective design measures and non-use of efficient and durable protective coatings. All these ‘causes of corrosion failure could be avoided. For this purpose newer corrosion resistant materials, better monitoring and detec- ‘ion techniques and technologies for repair and rehabilitation are the need of the hour. To meet these requirements, present investi- gations are directed towards the development of highly resistant ‘coating system for the protection of stect structures exposed to aggressive environment, In anti-corrosion coatings, use of epoxy resin dominates over ‘rier syathetic resins due to its superior strength, low shrink- ‘age, better bonding with different substrates, good dimensional stability and long term corrosion and chemical resistance [ Comesponsing aut, Tels 491 1582 283354: fk: 494 132 2722 pul aves thst yetmall som (8, Aggarwal). (0300-9405 - see front matey © 2007 Eber BW. Al rights reserved 4010-10464 poncot.2007.01.010 ‘These properties have prime importance inthe construction and building applications. The ambient curing epoxy systems werer- ally consist of wo components —a base comnponent and a curing ot hardener. The base component is epoxy resin, which is normally a standard liquid epoxy resin DGEBA, diglycidy! ether of bisphenol-A (a condensation product of bisphenolA and epichlorohydrin), The room temperature curing agents that are generally used with epoxy cesin to initiate the crosslinking are polyainines, polyamides and their addicts [4,5]. One probe Jem with the coatings made with epoxy resin is that they are rigid and have limited deformability, {¢ does not help in scess relaxation during their service life and may fail due 10 cracking To overcome this problem and to achieve other desired proper lies epoxy resin is often mioditied with different other poly icrie ‘compounds, such as coal tar{6.7], cashew nut shell liquid [8-11] phewotic and ether resins [12-14]. In this study, an attempt has been made to modify an epoxy resin with a eardanol resin for improving ity physica properties and chemical resistance, The modilied 1esin wes synthesized using epichlorohydrin, eardanel and bisphenol-A and designated as epoxy-cardanol resin, Propenies of the oxo resins, epoxy-cardanol and unnodified epoxy. were evaluated boy dotermining their physico-nechanical and chemical resis- {anee properties, Paints were formulated using the developedELK. Aggarwal etal /Progves in Organic Contngs $9 (2007) 76-80 epoxy--cardanol and the unmoditied epoxy resins with pigments, additives and aromatic polyamine adduct as a hardener, The developed paints were evaluated for their physico-mechanical properties, chemical resistance and corrosion. protection elfi- ciency, ‘The paper reports the outcome of the study in two parts. The Hirst part relates to the synthesis and evaluation of the modi- fied epoxy resin and the second deals with the formulation and evaluation of the formulated anticorrosion paints, 2. Synthesis and evaluation of resins 2.1. Symuheris of resins A modilied epoxy resin was synthesized using epichlorahy rin, bisphenel-A and cardanol as main raw materials. Glycidy! ether of cardanol was obtained by reacting epichlorohydrin and cardanol, and a prepolymer of epoay tesin DGEBA by reacting epichlorohydrin and bisphenol-A. The reactions were varried out i an inert atmosphere at about 150°C. The two resins thus ‘obtained were mixed in predetermined ratio and heated at about 60°C under controlled conditions. The resin so obtained was designated as epoxy-cardanol resin, The epoxy equivalent weight of the epoxy-cardanol resin was 210-230, viscosity 5000-6000 mPa$ at 25°C and density 1.05 g/cm’. ‘The unmodified epoxy resin had an epoxy equivalent ‘weight of 180-200, viscosity 8000-10,000 mPa at 25°C and density 1.15 g/cm’, An aromatic polyamine ndduet based hard- ‘ener was used with these resins. This hardener had an amine value of 320-340, viscosity 3000-5000 mPa at 25 °C and dene sity 110 g/em*. 2.2. Preparation of test samples Id steel and 5 85 panels of 150mm x 100 mm size were used and prepared according to the method given in IS: 101 Part See. 3: 2001 [15]. The steel panels were made free from oil and grease by cleaning them with xylene and then brushed uni- formily with an emery cloth of IS Grit No. 180. Traces of emery ddust were removed by wiping with a linen rag and swapped with «linen rug pre-soaked in a hydrocarbon solvent to degrease the panels. Then the panels were dried to remove the traces of con- dlensed moisture. The glass panels were degreased and dried in «Similar way, Two coats of each resin were applied on the thor: oughly cleaned steel and glass panels using a paintbrush, The coated panets were left in the laboratory for 7 days to ensure full drying and curing of te tims. The edges of the see! panels Were then seated with wax to prevent attack frorn the edges. At least thee stect panels were prepared for each chemical resis- tance and humidity cabinet test. To obtain free film properties, the films were carefully removed from the coated glass pancls, 2.2. Testing of the coatings Free film properties of the coatings, such as tensile strength, elongation and water vapour transmission were measured as per ‘ASTM-D-2370-1992 [16] and ASTM-D-1653-1993 | 17]. Bond Table 1 Properties of the epoxy andthe epony-cunlanol coatings Proper Epoxy-zandana Tensile strength (Naa) 2S Elongation (5) 6s Specitc permeability v.40 (inglcm? mm 24) Hardness, Shore D saxo ‘Shear tenth (Némm) 70 Vieat soften pont) ©) eh ‘Adhesion (bond strengih) with steel 32 «Nnm!) Seratch hardness. 151 hod No illuie Statue oetheient of ternal expansion 86 mH (0° per Cp Scrub resistance, 1,000 eyetes No tilare No tai Sale spray 1000, No vous sos Fes cumini strength was measured by the pull out method as per BS: 3900-L: 10-1979 [18] using a Dyna Procey adhesion tester, while setaich hardness and adhesion and fexibility were determined using the ‘coated stee! panels according to the method given in I$: 101 Past ses: 1 and 2: 1988 [19] 24, Results Results ofthe above studies show that the mivdilacation nf the aditiona epoxy resin with a curdhanol resin improves properties of the fin, For example. tensile strength and elongation ave increased while water vapour transinission decreased (Table |), The coefficient of thermal expansion became com paruble with that of the concrete, which is 6.1% 10° to 12.2» 10° per C (20), These results indigate that the coadiny bused un the modified resin would be moe effective and durable as compared tothe epoxy based couting. Itneans that the modified resin gould bea better binder for paints 3. Formulation and evaluation of paints Bul. Formulation of paints Paints were formulated using pigments like synthetic ison oxide, zine phosphate (ZnP), zine powder, micaceous iron oxide (MIO), blank fixe, calcite, magnesium silicateand titaniyin diox- ide along with other additives and solvents, Epoxy-vardano! resin with the aromatic polyamine adduct based hardener and unmodified epoxy resin with the same hardener were uses) us binders. The pigment volume concentration of the paints was kept at about 25% except that af the zine powder based pats for which it was 70%, The compositions of various paint fori lations used are given in Table 2 3.2, Preparation of the test sumptes Mild steel and glass panels were prepared as discussed in Section 2.2 above, The panels thus prepared were coated wrth the developed paints for carrying wut laburatory tests, Two coats8 LK: Aggarwa eat. / Progress i Osun Coatings $9 (2407) 76-80) “able 2 Compostion ofthe paints Palnc designation PVC Epoiy-carcanot Epoxy 4%) resin resin Zine poser 7% & Zine phosphate nen oxide Zz 4 tues tom anid 3 OM M, Micuccous won aside Fak we 28 My My of cach paint were applied on the steel und glass panels using paintbrush, The coated steel panels were used for determination of resistance of coatings against various exposure conditions, Whilst the glass panels were used to obtain free filins lot dif- ferent tests, The couted panels were left in laboratory for 7 days to ensure full drying and the curing of the paint films The edges of the steel panels were sealed with wax to prevent the ingress of chemicals from the edges, At least three pan- els were prepared for each test. The properties like coverage, drying time and fin thickness of different paints are given in Table 3 3.3. Testing of the painas 3.1. Physico-mechanical properties of the paints Physico-mechanical properties ofthe paints were determined following the procedure mentioned in Section 2.3 $3.2. Immersion test The chemical resistance behaviour of the paints was stud- ied by an immersion test, in which the painted. steel panels were placed vertically in 3000 ml glass beakers containing dif. ferent reagents. sch as water, 5% sodium chloride (NaC), saturated solution of urea and di-ammonium phosphate (DAP) for 180 days. The panels were examined at regular inter- vals to evaluate the degree of attack on the paint films and ‘on the substrate. For this purpose, the panels were taken out at different intervals, washed with water and visually exam- ined for the film integrity. overall appearance and any paint failure. Table 3 Properties of different pias Paint gaien — Gonenige -y lh Drying: tine cnt ickmess um) “Touch dey Hand usin ay th) q 43-50 0 Ww e 45-50 0 os a 50-55 8 45 a 3035 R845 ps 45 Mt ass0 0 gs4s as 38 Ms SUSS BS aS 8S 55 My 1550 45 a 2 Me SSS 4S Bs 2 “Table $ ree fi propetiest Pasa “Teasile strength Elongation WV sample (Nin) co Langone am 2589) a are 1835 wo a 13.09) 13st «8 M 328 20.13 as Mi: 110 lesa om My io 210 oat Ma 198 iaa7 pa AU valde the wea of Bve vBSEVations 333. Humidity eabinet test The stecl panels coated with different paints were kept in 8 corrosion cabinet maintained at about 100% relative humid ity and temperature in the range of 42-48 C as per IS: 101 Part 6/Sec. 1; 2000 [21]. Observations were recurded al regular intervals for any sign of deterioration of paint hms during the 180 days of exposure. The panels were tuken out of the cab het, washed with the water and visually examined for any paint failure Set. Results and eiscussion The results Of the tensile strength. elongation, water vapour transmission of the free films and the bond strength, scratch hardiess and flexibility, and udhesion are given an ‘Tables 4 and 5, respectively. Chemical resistance results are given in Tables 6 und 7, while the humidity cabinct test results are given in Table 8 34.1, Phyiico-mechanicul properties of te pe Physical properties of the paints like drying tinie. coverage and film thickness are given in Table 3, It can be nated that the panels Were coated with a similar thickness ofthe pants as dry film thickness of all the paints was 83-5 jum, The touch dry time for different paints varied frorn 28 to 35 min, white hard ‘dry time varied trom 45 10 SSh, Broadly the covering eapacity ‘ofthe paints varies from 4.5 10 5.5 m/ Tensile strength, elongation and water vapour taansmission sdatais given in Table 4. The tensile test data for paints Z1 and Zz could not be recorded. because these paint fils s¥ere very ints Table $ Properties ater aplication in the wee! sabstrate Paint Bondywengt? —_Adiesionand Seva mane sample (Ninn?) Aeuiility 82mm 500g weight ameter mand 4 iat No falure Na tailure 2 19s Nosfulure No ature zs 279 No tature No taline 4 2a No failure Natale My 27 No alte No tule Ms 229 No fituce Xo failure My 286 Notatore Noite Me 237 No tuluse Nostale i ean OF fie obscrsuionsLK: Aggarwal eval. / Progress in Organ Couings $9 (2007) 76-80 w fable sults of the water and youu chore inmersion teste—L80 days Water immeiion Soins ehloride (%) soutien a Blisers throughout the panels Biter rough oat the panel ‘ister eroughout the panels) Blisters through out ap n Small blisters (10% area) Small blisters (159% sea) x Blisters ehvough out und Blisters, thoughout My No signs of put failure ‘No sins of pot file My Blisters (15-209 area) Blisters, through othe panels My eve sna blisters Few spall Wists M. Small blisters through ot the Blisters through wut the panics prs fate Resuls of he wee and 8 annuiniue phayphate immersion testo—180 days Poiorsumple Urea solution immersion ‘Di-ammonium phosphate latin inmersion a ‘Sina liens in 10% age ‘Blisters thugh out the panels Blisters and few corrosion Smal bsters through out spots the panels Few small blisters Blisters in 255 No signs of pa fatave ‘Small blisters through ou the panels My Do signs of pal faiure No sigs of pint alae M, Sinal blister in 20% ate ‘Blisters tm 305% area Mi No signs of pain fa Few small blsers Mi Blisters in 75% aces De-bonuling of fi alter 30days britle and failed without significant elongation during the test. From Tables it can be noted that the tensile strength for the coat- ings Zs, Mj and Ms, which were Formulated using the modified resin are in the range of 16.71-18.28 Nimm?, while the tensile strength values for unmodified resin based paints, Z4, My and Ms sary between 13.09 and 14.1 N/mm?. It shows that the modified resin based paints exhibit about 25% higher tensile strength than the paints made with unmoditied resin. Sinitarly elongation for the epoxy-cardanol resin based pains is about 15% more than Table § Results uf the humility cabinet test 180 days exposure ‘Observations al listers (2558 area) nl listers though out nd few corronion spots a No signs of paint failure 4 Saul blisters ™ [No signs of paint tre M: Soul isters (30% area) My Sonal blisters (105% area) Me ‘Smal blsiers throughout aad few that uf unmoditied resin based paints indicating bore flesibility, he values of water vapour transmission (WV) of moxilied resin bused paints is about 20% lower than that of unuualifiea resin based paints (Table 4). The above-mentioned results shor that the free film properties of modified resin buseul paints are superior to that of unmodified resin based paints, Furthermore. paint films based un micaceous jon oside and zane phosphate show the highest tensile strength and minimum water vapour transmission, so these paints should have better performance compared to the other formulated paints Properties of the paints afier the application on the substrate Bond strength values of different paints are given in Table 5 The bond strength of the mosditied resin bused paints ate ia the range of 2.32-2.86 Nimm? and for epoxy resin it is in the range of 1.98-2.41 N/mm, i. the bund strength for the modified resin is about 15% higher. During the test, it was observed that the paint bused on the mewlfied resin failed cobesively (fanlore m the paint film) while it was adhesive bond fature Uailae bere the paint film and substrate} in case of unmodified resin hased paint fms, at relatively low stress level, Amongst the forms fated paints, MIO and aie phsphate based pals show beter sudhesion properties as compared to zine powder bused paints and the bond strength of MIO based paints in modified aesin is the highest followed by zine phosphite based paint «Table 5) In adhesion and Mesibilily test the eoated panels jected to bending using # mandrel of 3.2mm diameter und the results obtained forthe different paints are given in Vable 5, The paint filns showed no signs of damage. detachment or crackit after the test indicating good flexibility, the elongation pf the paint lis is about 28% as per ASTM D $22.93 (22). Thete- fore. the elongation values forthe attached paint film were higher ‘as compared to the elongation of the free films of the pants 13.51-21,01% (Table 4), All the paints pass the scratch hid fess test When tested using a weight of 1500 g (Table 5) showing ‘good abrasion resistance sete sub 34.3. Chemical resistance tests wemical resistance test results are reported in Tables G.and 7, {In water inninersion test, paint My showed no sign of disintegra tion while My and Z showed few small blisters. Paints, Z2. Zs and My showed medium dense blisters of average size und pre ence of corrosion. Zs showed maximum comoded area of about 10%, These results show that the performance of the micaceaus iron oxide based paints in moditied resin is the best followed by zine phosphate based paint in the same resin. Simitay wend is observed when the painted panels were imunersed laa 9% sodium chloride solution for 180 days. ie, My aid My paints showed the best performance followed by 2, Panel costed sath My; paint is not affected while others show signs of talue ot paints In urea and di-ammoniam phosphate solution immersion tests, paint My showed the best performance followed by Zs and M5 paints. Other paints showed considerable blistering suxiéor corrosion (Table 7), In these tests also micaceous iron oxide and zine phosphate based paints in inodified resin, i.e. the pailsy so LAK, Aggarwal er. Progress in Onsunte Courngs $9 2007) 76.80 bused on the modified epoxy resin showed superior performance, Big size blisters appeared in the paint My within 15 days and the coating completely pected off after 30 days of exposure. On the basis ofthe above results it can he inferred that the performance ‘of the modified resin based paints is superior to the unmodified epoxy resin based paints. SAA, Humidity cabinet test Results of the humidity cabinet exposure test are given in Table 8, In this test, Zs and My paints showed the best results, as no signs of faifure was observed in these pain fils up to 180 {days of exposure. followed by Ms with few small listers on the panels, Paints Z2 and My showed small blisters throughout the panels along with few corrosion spots, while Z; and Zs paints showed small blisters Strength and permeability of the paints film are important fac- tors for the antivorrosive efficiency of the paints, In the present investigations paint M, with the highest strength and the lowest petmieability amongst the forniulated paints showed minimum blistering in immersion and humidity cabinet tests, ie. the best {iim integrity and appearance, while the pain’ My having the lowest strength and highest permeability showed maximum blis- tering. The corrosion of the substrate is minimum in My and ‘maximum in My, with the exception of Zin the water immer- sion test. Hence, the anticorrosive behaviour of the paints has Sone relation to their strength and permeability properties. 4, Conclusions The results of the above studies show that the modification of epoxy resin with a cardanol resin has resulted into improvement nits properties, Anticorrosive properties ofthe epoxy-cardanol résin based paints are superior to that uf paints formulated using the unmodified epoxy resin, imespective of the pigments, fillers and the additives used. Therefore, the developed resin isa better binder media forthe formulation of anticorrosion paints than the unmodified epoxy resin. Amongst the formulated paints, paint Mj exhibited excellent properties with respect to film integrity and overall appearance. 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